Vibratingly stirring apparatus, and device and method for processing using the stirring apparatus

ABSTRACT

An insulated vibration-stirring apparatus comprising a vibration generating means containing a vibration motor and a vibrating member attached to that motor, and a vibrating rod attached by an installation piece to allow vibration linked with the vibration generating means, and vibrating vanes installed on this vibrating rod. An electrical insulation area made from hard rubber is installed on a section nearer to the installation section to the installation piece than the section where the vibrating vanes are mounted on the vibrating rod. An electrical line is connected to the lower section of the vibrating rod on the electrical insulation area side where the vibrating vanes are installed. This electrical line conducts power to the vibrating vanes by way of the lower section of the vibrating rod. A power supply applies a voltage across the lower section of the vibrating rod and vibrating vanes and treatment tank by way of the electrical lines, and while applying power to the processing liquid within the treatment tank, the insulation vibration stirring apparatus vibrates and stirs the processing liquid.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a novel vibration stirringapparatus incorporating functions of both an electrode and a coolingmeans, and to a device and method for processing liquids or productsutilizing a vibration stirring apparatus. The present invention is forexample ideal for surface treatment of products of all types byelectrolysis.

[0003] 2. Description of Related Art

[0004] In vibration stirring devices, vibrating vanes are mounted on avibrating rod and the vibrating rod then oscillated to make the vanesmove in a fluid such as a liquid and in this way create fluid motion.This kind of vibration stirring apparatus is disclosed in the followingpatent documents in Japanese patent application for inventions by thepresent inventors.

[0005] JP-A No.275130/1991 (Patent No. 1941498)

[0006] JP-A No.220697/1994 (Patent No. 2707530)

[0007] JP-A No. 312124/1994 (Patent No. 2762388)

[0008] JP-A No.281272/1996 (Patent No.2767771)

[0009] JP-A No.173785/1996 (Patent No.2852878)

[0010] JP-A No.126896/1995 (Patent No.2911350)

[0011] JP-A No.189880/1999 (Patent No.2988624)

[0012] JP-A No. 54192/1995 (Patent No. 2989440)

[0013] JP-A No.33035/1994 (Patent No.2992177)

[0014] JP-A No.287799/1994 (Patent No.3035114)

[0015] JP-A No.280035/1994 (Patent No.3244334)

[0016] JP-A No. 304461/1994 (Patent No. 3142417)

[0017] JP-A No.43569/1998

[0018] JP-A No.369453/1998

[0019] JP-A No.253782/1999

[0020] Vibration stirring apparatus are used in different types ofprocesses. The basic function of these vibration stirring apparatus isto generate a vibrating movement in the fluid. In recent years however,functions other than this basic function are being added to thevibration stirring apparatus.

[0021] An electrolytic polishing method for aluminum products wasdisclosed in the invention of JP-A No.199400/1996. This method wascharacterized by utilizing for example, titanium alloy electrodes orvanes made of titanium capable of generating fluid flow accompanying thevibration of electrolytic fluid by causing vertical (up/down) vibration.This invention however did not disclose whether the vibrating rod wasutilized as electrodes or the vanes were utilized as electrodes. Furtherthere was virtually no specific description of how electrical insulationwas maintained between the sections utilized as electrodes and the othersections. An examination of the overall description indicates that thevibrating rod might be utilized as the electrode. However there are nodescriptions or suggestions whatsoever of how the vibration motor isinsulated when electrical current flows in the vibrating rod and howsafety was maintained.

[0022] A method was disclosed in JP-A No. 125294/1997 for a surfacetreatment device comprised of a vibration stirring apparatus utilizing asupport rod as the electrode. However in this invention also there wereno descriptions or suggestions whatsoever of how the overall vibrationstirring apparatus and electrodes were electrically insulated. Further,in this disclosure of technology of the known art, the electricalcurrent density was 3 mA/cm² which is approximately the same electricalcurrent density as ordinary plating (or galvanizing).

[0023] When the vibration stirring apparatus is agitating a high or lowtemperature fluid, heat is propagated by the vibration generating meanssuch as the vibration motor, and the fluid by way of the vibrating rod.This fluid might subject the vibration generating means to heatexpansion and eventually cause a drop in performance.

SUMMARY OF THE INVENTION

[0024] In view of these problems, it is an object of the presentinvention is to expand the applicable range of the vibration stirringapparatus by adding functions different from its basic function, and tofurther improve performance unique to that applicable range.

[0025] One applicable range is surface treatment. This surface treatment(processing) encompasses the following technical problems.

[0026] In current technical fields for example for anodic oxidation,plating, and electro-deposition utilizing electrolysis, the electricalcurrent density varies somewhat according to the type of processingfluid (electrolyte), and the purpose or other equipment but is usually 2to 3 A/dm². The crystallizing speed of the electrical plating isproportional to the electrical current density. A means is known in therelated art for high speed plating by utilizing a powerful pump to sprayelectrolytic fluid on the item for processing (treating) and thereforeincrease the electrical current density. Even with this method however,the electrical current density is limited to only about 5 to 6 A/dm².Also, irregularities occur in the product film thickness so this methodis not practical to use.

[0027] In regions with low electrical current density, the current flowis highly efficient at nearly 100 percent. But when the electricalcurrent density exceeds a certain point, the electrical currentefficiency suddenly drops and hydrogen gas generated from the platingsurface can be observed. When the electrical current density increaseseven further, the pH rises in the electrode boundary, unwanted secondaryreactions occur in the electrode boundary, bubbles are generated,electrical current stops flowing and the (desired) reaction progressesno further.

[0028] The electrical current density therefore has an upper limit or inother words a threshold current density. Trying to raise the electricalcurrent density further than this limit to speed up the processing byshortening the gap (distance) between electrodes, causes burning andscorching on the product and a flat, smooth and uniformelectrodeposition surface cannot be obtained.

[0029] In the field of electroforming, and even in the so-calledhigh-speed electroforming plating method, this current density thresholdis approximately 30 A/cm². Irregularities of approximately ±8 to 10micrometers also occur in the film thickness.

[0030] In all of these surface treatment methods, the stirring (oragitating) apparatus is installed based on the concept that stirring foruniformity in the processing fluid can be acheived by not closelyapproaching the article (liquid and article) (treating). Use ofvibration stirring apparatus also follows this same approach and sothere is no concept of using small gaps (distances) between the stirringapparatus and article (liquid and article), or between the stirringapparatus and electrodes. In other words, the article (liquid andarticle) and vibration stirring apparatus are not installed facing eachother. Further, one end of the anode is installed at a position very faraway from the vibration stirring apparatus. The installation of thevibration stirring apparatus is therefore only concerned with uniformity(consistency) in the agitation (stirring) of the processing fluid.

[0031] An electrodeposition coating device and electrodeposition coatingmethod utilizing a vibration stirring apparatus are disclosed in JP-ANo. 87893/1997. According to the description of the invention, the itemsfor coating pass continuously along a long and narrow electrodepositioncoating tank so the vibration stirring apparatus is installed near thetank inlet area. The next area is an electrodeposition coating areaformed from side electrode plates and diaphragm enclosing theseelectrodes. Even in this kind of electrodeposition coating, there is noconcept in the conventional art for installing the stirring apparatus asclose as possible to the electrodes or items for processing.

[0032] An electrodeposition coating device and electrodeposition coatingmethod utilizing a vibration stirring apparatus are also disclosed inJP-A No. 146597/2002. Here also, there is no concept for installing thevibration stirring apparatus as near as possible to the electrodes andobjects for processing.

[0033] A further object of the present invention is to provide ahigh-speed surface treatment apparatus and high-speed surface treatmentmethod for drastically increasing the conventional electrical currentdensity threshold by reducing the gap between the electrode and objectto be processed, and also eliminating the occurrence of irregularitieswhen forming the film thickness, without causing scorching and burns andfurther without causing bubbles in the electrode.

[0034] To achieve the above objects of the invention, an insulated typevibration stirring apparatus is proposed comprising:

[0035] a vibration generating means and, at least one vibrating rod forvibrating while linked to the vibration generating means, and

[0036] at least one vibrating vane installed on the vibrating rod, andan electrical or heat-insulation area installed on a link sectionlinking the vibrating rod with the vibrating generating means, or on asection nearer the linking (connection) than the section where thevibrating vane is installed on the vibrating rod.

[0037] In the embodiment of the present invention, that insulation areais a material comprised mainly of (synthetic resin) plastic and/orrubber.

[0038] In the embodiment of the present invention, the insulation areais an electrical insulation area. An electrical line connects to thelower section of the vibrating rod on the side of the electricalinsulation area where the vibrating vanes are installed. In theembodiment of the present invention, the insulated type vibrationstirring apparatus contains a power supply connected to that electricalline.

[0039] In the embodiment of the present invention, the electrode memberis electrically connected to that electrical line installed on thatvibrating rod on the side of the electrical insulation area where thevibration vanes is installed. In the embodiment of the presentinvention, at least one vane of the vibrating vanes functions as anelectrode member.

[0040] In the embodiment of the present invention, auxiliary vibratingvanes-for-electrode electrically connected to the electrical line by wayof the vibrating rod are installed on the vibrating rod on the side ofthe electrical insulation area where the vibrating vanes are installed.In the embodiment of the present invention, electrode support vanes areinstalled on the vibrating rod so that the electrode support vanepositions alternate with the vibrating vane positions. In the embodimentof the present invention, the surface area of the electrode supportvanes is larger than the surface area of the vibrating vanes, and thetips of the electrode support vanes protrude farther than the tips ofthe vibrating vanes.

[0041] In the embodiment of the present invention, a first electrodemember and a second electrode member forming a pair of electrode membersare respectively connected to multiple vibrating rods, and the firstelectrode member is electrically connected with the electrical line byway of at least one of the multiple vibrating rods, and the secondelectrode member is electrically connected with the electrical line byway of at least one other of the multiple vibrating rods.

[0042] In the embodiment of the present invention, the gap between thefirst electrode member and the second electrode member is maintained at20 to 400 millimeters. In the embodiment of the present invention,vibrating vanes are installed on multiple vibrating rods, and at least aportion of the vibrating vanes function as the first electrode member oras the second electrode member.

[0043] In the embodiment of the present invention, each of the multiplevibrating vanes are installed on the multiple vibrating rods, and aportion of the multiple vibrating vanes function as the first electrodemember and, another portion of the multiple vibrating vanes function asthe second electrode member. In the embodiment of the present invention,electrode support vanes are installed on the multiple vibrating rods onthe side of the electrical insulation area where the vibrating vanes areinstalled, and the electrode support vanes function as a first electrodemember or a second electrode member.

[0044] In the embodiment of the present invention, multiple electrodesupport vanes are installed on the multiple vibrating rods on the sideof the electrical insulation area where the vibrating vanes areinstalled, and a portion of the electrode support vanes function as thefirst electrode member and, another portion of the multiple electrodesupport vanes function as the second electrode member.

[0045] In the embodiment of the present invention, the insulation regionis a heat insulation region, and a heat exchange medium injector sectionand a heat exchange extraction section are installed on the side of theheat insulation area where the vibrating vanes are installed on thevibrating rod.

[0046] To achieve the above objects, the present invention provides, aliquid treatment apparatus for an insulated vibration-stirring apparatuscomprising a vibration generating means and, at least one vibrating rodfor vibrating while linked to the vibration generating means, and atleast one vibrating vane installed on the vibrating rod, and anelectrical insulation area installed on a link section linking thevibrating rod with the vibrating generating means, or installed nearerthe linking (connection) than where the vibrating vane is installed onthe vibrating rod;

[0047] and further comprising a treatment tank for holding theprocessing liquid, and

[0048] a first electrode member and a second electrode member forming apair, and

[0049] a power supply for applying direct current, alternating currentor pulsed voltages across the first electrode member and the secondelectrode member.

[0050] In the embodiment of the present invention, a gap of 20 to 400millimeters is maintained between the first electrode member and thesecond electrode member.

[0051] In the embodiment of the present invention, an electrical line iselectrically connected to the side of the electrical insulation areawhere the vibrating vanes are installed on the vibrating rod, and thefirst electrode member or the second electrode member are installed onthe side of the electrical insulation area where the vibrating vanes areinstalled on the vibrating rod, and further are electrically connectedto the power supply by way of the vibrating rod and the electrical line.

[0052] In the embodiment of the present invention, the vibrating vaneselectrically connected with the power supply by way of the vibrating rodand the electrical line are installed on the side of the electricalinsulation area where the vibrating vanes are mounted on the vibratingrod, and function as a first electrode member or as a second electrodemember. In the embodiment of the present invention, the electrodesupport vanes are electrically connected with the power supply by way ofthe vibrating rod and the electrical line, and function as the firstelectrode member or as the second electrode member. In the embodiment ofthe present invention the liquid treatment apparatus comprises twoinsulated vibration-stirring apparatus; and the power supply applies avoltage across a the first electrode member of one insulatedvibration-stirring apparatus, and a second electrode member of the otherinsulated vibration-stirring apparatus.

[0053] In the embodiment of the present invention (liquid treatmentapparatus), vibrating vanes are installed on the multiple vibratingrods, and each of the first electrode members and the second electrodemembers are installed on the multiple vibrating rods, and the firstelectrode members are electrically connected with the power supply byway of at least one of the multiple vibrating rods and the electricalline connected to the vibrating rods, and the second electrode member iselectrically connected with the power supply by way of at least one ofthe other the multiple vibrating rods and by the electrical lineconnected to the vibrating rods.

[0054] In the embodiment of the present invention liquid treatmentapparatus), at least one of the multiple vibrating rods and thevibrating vanes electrically connected with the power supply by way ofan electrical line connecting to the vibrating rod functions as thefirst electrode member, and/or at least one of the other multiplevibrating rods and the vibrating vanes electrically connected with thepower supply by way of an electrical line connecting to the vibratingrod functions as the second electrode member.

[0055] In the embodiment of the present invention a (liquid treatmentapparatus), electrode support vanes are installed on the multiplevibrating rods on the side of the electrical insulation area where thevibrating vanes are installed, and at least one of the multiplevibrating rods and the electrode support vanes electrically connectedwith the power supply by way of an electrical line, functions as thefirst electrode member, and/or at least one of the other multiplevibrating rods and the electrode support vanes electrically connectedwith the power supply by way of an electrical line, functions as thesecond electrode member.

[0056] In the embodiment of the present invention liquid treatmentapparatus), electrode support vanes are installed on the multiplevibrating rods on the side of the electrical insulation area where thevibrating vanes are installed, and at least one of the multiplevibrating rods and the electrode support vanes electrically connectedwith the power supply by way of an electrical line, functions as thefirst electrode member, and/or at least one of the other multiplevibrating rods and the electrode support vanes electrically connectedwith the power supply by way of an electrical line, functions as thesecond electrode member.

[0057] To achieve the above objects, the present invention provides aliquid processing method, wherein a processing liquid is filled into thetreatment tank of a liquid treatment apparatus, the vibrating vanes areimmersed in the processing liquid, and the vibrating vanes are made tovibrate while power is conducted across the first electrode member andthe second electrode member by way of the processing liquid.

[0058] In the embodiment of the present invention (liquid treatmentapparatus), a gap of 20 to 400 millimeters is maintained between thefirst electrode member and the second electrode member. Also in theembodiment of the present invention, the vibration generating meansvibrates at a frequency of 10 to 500 Hz; the vibrating vanes have anamplitude of vibration of 0.1 to 30 millimeters and further are made tovibrate at a frequency of 200 to 12,000 times per minute.

[0059] In the embodiment of the present invention, members on thevibrating vane side of the electrical insulation region on the vibratingrod in the vibration-stirring apparatus are utilized as at least one ofeither the first electrode member or the second electrode member. In thepresent embodiment, vibrating vanes are utilized as at least one ofeither the first electrode member or the second electrode member.

[0060] In the embodiment of the present invention, electrode supportvanes installed on the vibrating vane side of the electrical insulationregion on the vibrating rod in the vibration-stirring apparatus areutilized as at least one of either the first electrode member or thesecond electrode member.

[0061] The embodiment of the present invention, uses two insulatedvibration-stirring apparatus, and a member installed on the vibratingrod of the first vibration-sting apparatus is utilized as the firstelectrode member, and a member installed on another vibrating rod of thesecond vibration-stirring apparatus is utilized as the first electrodemember.

[0062] In the embodiment of the present invention, vibrating vanes areinstalled on multiple the vibrating rods in the vibration-stirringapparatus, and members installed on the vibrating vane side of theelectrical insulation region on the multiple vibrating rods in thevibration stirring apparatus are utilized as at least one of either thefirst electrode member or the second electrode member, and at least oneamong the multiple vibrating rods functioning as the first electrodemember are electrically connected to the power supply, and at least oneamong the other multiple vibrating rods functioning as the secondelectrode member are electrically connected to the power supply. In theembodiment of the invention, at least one of either the first electrodemember of the second electrode member are utilized as the vibratingvane.

[0063] To achieve the above objects, the present invention provides: asurface treatment apparatus comprising:

[0064] a treatment tank;

[0065] a vibration-stirring apparatus (A) containing; a vibrationgenerating means, at least one vibrating rod for vibrating while linkedto the vibration generating means, and at least one vibrating vaneinstalled on the vibrating rod;

[0066] an electrode member (B); and

[0067] a holder for maintaining a product for processing (C) to allowelectrical conduction,

[0068] wherein the vibrating vanes, the electrode member (B) and theproduct for processing (C) are installed within the treatment tank tomaintain a respective gap of 20 to 400 millimeters.

[0069] In the present invention, the holder for maintaining the productfor processing (C) to allow electrical conduction, is not limited to aholder that forms a conductive path to the product for processing (C)from a power supply connected electrically the product for processing(C); and the product for processing (C) maintained by the holder mayconnect to a power supply by way of a conducting path installedseparately from the holder.

[0070] In the embodiment of the present invention, the electrode member(B) and the product for processing (C) are installed to face the tip ofthe vibrating vane. In the embodiment of the present invention, theelectrode member (B) is made from a porous plate piece, a web-shapedpiece, a basket-shaped piece or a rod-shaped piece.

[0071] To achieve the above objects, the present invention provides: asurface treatment apparatus comprising

[0072] a treatment tank;

[0073] a vibration-stirring apparatus (A′) containing; a vibrationgenerating means, at least one vibrating rod for vibrating while linkedto the vibration generating means, and at least one vibrating vaneinstalled on the vibrating rod, and an electrical insulation area isinstalled at a link section linking the vibrating rod and the vibrationgenerating means, or on a section nearer the linking (connection) thanthe section where the vibrating vanes are mounted on the vibrating rod;

[0074] a holder for maintaining a product for processing (C) to allowelectrical conduction,

[0075] wherein the vibrating vanes, and the product for processing (C)are installed within the treatment tank to maintain a respective gap of20 to 400 millimeters.

[0076] In the embodiment of the present invention (surface treatmentapparatus), the product for processing (C) is installed to face the tipof the vibrating vane. An embodiment of the present invention furthercomprising an electrode member (B), and the electrode member (B) isinstalled within the treatment tank to maintain a respective gap of 20to 400 millimeters with the vibrating vane and the product forprocessing (C). In the embodiment of the present invention, theelectrode member (B) is made from a porous plate piece, a web-shapedpiece, a basket-shaped piece or a rod-shaped piece.

[0077] In the embodiment of the present invention, the insulation areaof the insulated vibration-stirring apparatus (A′) is a materialcomprised mainly of plastic and/or rubber. In the embodiment of thepresent invention, on the insulated vibration-stirring apparatus (A′),an electrical line is connected to the vibrating rod on the side of theelectrical insulation area where the vibrating vanes are installed.

[0078] In the embodiment of the present invention, electrode supportvanes are installed on the vibrating rod on the side of the electricalinsulation area where the vibrating vanes are installed. In theembodiment of the present invention, electrode support vanes areinstalled on the vibrating rod so that the electrode support vanepositions alternate with the vibrating rod positions. In the presentembodiment, the surface area of the electrode support vanes is largerthan the surface area of the vibrating vanes, and the tips of theelectrode support vanes protrude farther than the tips the vibratingvanes.

[0079] To achieve the above objects, the present invention provides: asurface treatment method, wherein a processing liquid is filled into thetreatment tank of a surface treatment apparatus, the vibrating vanes,the electrode member (B) and the product for processing (C) are immersedin the processing liquid, and the electrode member (B) is set as oneelectrode, and the product for processing (C) is set as the otherelectrode, and the vibrating vanes are made to vibrate while power isconducted across one electrode member and other the electrode member byway of the processing liquid.

[0080] In the embodiment of the present invention, the surface treatmentmethod is electrodeposition, anodic oxidation, electropolishing,electro-degreasing, plating or electroform plating or is preprocess orpostprocess using these methods. In the present embodiment, theelectrodeposition, anodic oxidation, electro-degreasing,electropolishing, plating, preprocessing or postprocessing for thesemethod, or preprocessing or postprocessing for electroform plating isperformed at an electrical current density of 10 A/dm² or more. In thepresent embodiment, the electroform plating is performed at anelectrical current density of 20 A/dm² or more. In the presentembodiment, the vibration generating means vibrates at a frequency of 10to 500 Hz; the vibrating vanes have an amplitude of vibration of 0.1 to30 millimeters and further are made to vibrate at a frequency of 200 to12,000 times per minute.

[0081] To achieve the above objects, the present invention provides: asurface treatment method wherein a processing liquid is filled into thetreatment tank of a surface treatment apparatus, the vibrating vanes andthe product for processing (C) are immersed in the processing liquid,and the vibrating rod and the vibrating vane electrically connected tothe vibrating rod are set as one electrode, and further, the product forprocessing (C) is set as the other electrode; and the vibrating vanesare made to vibrate while power is conducted across one electrode andother the electrode by way of the processing liquid; and product forprocessing (C) is surface treated.

[0082] In the embodiment of the present invention, the electrode member(B) is installed within the treatment tank to maintain a respective gapof 20 to 400 millimeters with the vibrating vane and the product forprocessing (C); and the electrode member (B) is utilized as the otherelectrode.

[0083] In the present invention, the structure of the insulated typevibration stirring apparatus (A′) is included among the structures ofthe vibration stirring apparatus (A).

[0084] In the present invention, the arrangement sequence for thevibration stirring apparatus (A), the insulated type vibration stirringapparatus (A′), the electrode member (B) and the product for processing(C) may for example include the following.

[0085] (A)-(B)-(C)

[0086] (B)-(A)-(C)

[0087] (A)-(B)-(C)-(B)-(A)

[0088] (B)-(A)-(C)-(A)-(B)

[0089] (A)-(B)-(C)-(A)-(B)

[0090] (A′)-(B)-(C)

[0091] (B)-(A′)-(C)

[0092] (A′)-(B)-(C)-(B)-(A′)

[0093] (B)-(A′)-(C)-(A′)-(B)

[0094] (A′)-(B)-(C)-(A′)-(B)

[0095] (A′)-(B)-(C)-(B)-(A)

[0096] (B)-(A′)-(C)-(A)-(B)

[0097] (A′)-(C)

[0098] (A′)-(C)-(A′)

[0099] (A′)-(C)-(B)-(A′)

[0100] (A′)-(C)-(A′)-(B)

[0101] In the related art, there was no concept of installing thestirring apparatus near the electrodes and the product for processing.The reason there was no such concept was that bringing the stirringapparatus too close to the electrodes and the product for processingcreated “iregularities” in the liquid to be stirred within the treatmenttank so that the uniformity of the product processing might deteriorate.This concept was carried over to the vibration stirring apparatus.

[0102] However, the concept of the present inventors is contrary to therules used up until now for stirring or agitation. In this novelconcept, the vibrating vane or electrode support vanes in the vibrationstirring apparatus are installed facing and in proximity to the productfor processing (C) and the electrode member (B). When a liquid with astrong flow motion comes in contact with the opposing surfaces of theproduct for processing (C) and the electrode member (B), the surprisingresult was that no electrical short occurred between the two componentswithin a distance where electrical shorts were predicted to occur instirring in the conventional art. In other words, it was revealed thatat a distance considered as approximately 500 millimeters at most upuntil now, the electrical current density could be increased whilereducing the distance to 400 millimeters, preferably 300 millimeters,even more preferably 200 millimeters and most preferably approximately180 millimeters without causing an electrical short to occur. Howeverthe distance between the vibrating vane or electrode support vane, andproduct for processing (C) and electrode member (B) is preferably 20millimeters or more. If this distance is reduced to less than 20millimeters then electrical shorts might occur.

[0103] The distance at which the electrode member (B) and product forprocessing (C) are installed to face each other is preferably 200millimeters or less. This distance is more preferably 180 millimeters orless, and a distance of 100 millimeters or less is particularlypreferable. However this distance should not exceed 20 millimeters.

[0104] In the present invention, in vibration stirring apparatus (A) orinsulated type vibration stirring apparatus (A′), the distance betweenthe vibrating vane or electrode support vane, and the product forprocessing (C) or electrode member (B) here signifies the maximumdistance between the tip of vibrating vane or electrode support vane{protruding towards (C) or (B)} and the product for processing (C) andelectrode member (B) in the vibration stirring apparatus (A) orinsulated vibration stirring apparatus (A′).

[0105] In the present invention, it is extremely preferable that theproduct for processing is installed to face the vibrating vane orelectrode support vane of the vibration stirring apparatus (A) orinsulated vibration stirring apparatus (A′). Here, “to face” signifiesan installation position where the vibration flow motion generated bythe vibrating vanes of vibration stirring apparatus (A) or insulatedvibration stirring apparatus (A′) is conveyed directly to the surfacefor processing (In other words, the vibrating vane tip faces towards thesurface for processing on the product (C)). When the product forprocessing for example has a flat processing surface, this signifiesthat that the surface to be processed is installed to face the tip ofthe vibrating vane or electrode support vane. When the product forprocessing has a surface greater than more than one vibration stirringapparatus, then multiple vibration stirring apparatus may be arrayed atposition facing that surface for processing. When the product forprocessing is a small object, then that small object may be installed soit is entirely faced by the vibrating vanes or electrode support vanesof vibration stirring apparatus (A) or insulated vibration stirringapparatus (A′). The same technique may be utilized when the small objectis inserted into a barrel for processing.

[0106] In the present invention, the vibrating vanes mounted on thevibrating rod have an amplitude of vibration in the processing fluid orprocessing fluid within the treatment tank of 0.1 to 30 millimeters, andpreferably 0.1 to 20 millimeters, and more preferably 0.5 to 15millimeters, and most preferably 2 to 15 millimeters. The number ofvibration (frequency) is 200 to 12,000 times per minute, and preferablyis 200 to 5,000 times per minute and most preferably is 200 to 1,000times per minute.

[0107] The electrode member may for example have a porous plate shape, ametallic net shape, a basket shape (including metallic pieces ormetallic clusters within the basket) or a rod-shaped piece. The porousplate shape may for example be in the shape of a metallic net or mesh.The electrode member is preferably in a shape that avoids as much aspossible impeding the flow motion of the liquid.

[0108] The present invention can perform surface treatment processingsuch as electrodeposition, anodic oxidation, plating,electro-degreasing, electropolishing, and electro-cast plating. Theproduct for processing is an base object for coating/painting when usingelectrodeposition, a base object for anode oxidizing when using anodicoxidation, a base object for plating when using plating, a base objectfor degreasing when using electro-degreasing, a base object forpolishing when using electropolishing, and a base object for electroformplating when using electroforming.

[0109] The electrodeposition treatment (or processing) is performed thesame as in the related art according to the process ofdegreasing/washing/surface adjustment/film forming/washing/hot washing(drying away moisture)/electrodeposition/primary washing/secondarywashing/airblow/and tempering (annealing). The present invention isachieved through the electrodeposition process. Electrodeposition mayconsist of anion electrodeposition or cation electrodeposition. Thepresent invention applies to either type of electrodeposition andrenders the effect of greatly reducing the required time and alsoimproving the uniformity of the paint/coating film.

[0110] The anodic oxidation treatment process may use lead, carbon or ametal (for example, aluminum if the process is anodic oxidizing ofaluminum) identical to the anodic oxidized item as the cathode plate(electrode member) the same as in the related art. The vibrationstirring apparatus of present invention use the electrode members inclose proximity so preferably a porous type (Items arranged in a rodshape may also be used.) having holes formed at appropriate gaps or anet shape may be utilized as the cathode (negative electrode) plate.Pure titanium or titanium alloy is preferably utilized as the cathodeplate in view of its durability and resistance to corrosion. The productfor processing may be aluminum, or an alloy of aluminum (for example,Al—Si, Al—Mg, Al—Mg—Si, Al—Zn, etc.) magnesium or an alloy of magnesium,tantalum or an alloy of tantalum, titanium or alloy of titanium.

[0111] There are no particular restrictions on the processing fluid(processing liquid) utilized in the anodic oxidizing. However theprocessing liquid is preferably ammonium sulfate, alkali sulfate or anelectrolytic fluid containing a combination of these liquids. Morespecifically, the sulfuric acid is 0.3 to 5.0 moles per liter, theammonium sulfate is 0.16 to 4.0 moles per liter and/or the alkalisulfate is 0.1 to 2.0 moles per liter.

[0112] The electrical plating may utilize metal objects or plasticssubjected to activizing treatment as the product for processing.

[0113] The crystallizing speed during electrical plating is proportionalto the electrical current density so a larger electrical current densityis linked to a higher plating speed. The plating method of the relatedart had a limited electrical current density of about 2 to 4 A/dm² atmost. If the electrical current density is increased higher than this,the electrical current efficiency suddenly drops, hydrogen gas isemitted from the surface of the processed product in conspicuousamounts, the pH on the electrode boundary rises, and hydroxides settleinto the electrode surface. Countermeasures proposed to eliminate theseproblems included forced flow feed of plating fluid (parallel flowmethod, jet flow method, spray flow method, etc.) and the vibratingbarrel method for making solid particles. (for example, polishingparticles and glass spheres) strike the plating surface. However none ofthese methods proved satisfactory.

[0114] However when the present invention is used with this kind ofplating, the emission of hydrogen gas from the electrode member can besuppressed even if the electrical current density is increased. Forexample, even at a high electrical current density of 10 to 30 A/dm²,the electric current efficiency does not drop and high efficiencyplating can be performed. In particular, when using thevibration-stirring apparatus (A), the electrode member (B) is installedclose to the product for processing (C) on the stirring apparatus sideof (C) or opposite side, and a shape such as a rod, net, or net-basketshape is utilized as the electrode member (B) so that the electricalcurrent density is drastically improved.

[0115] The present invention is effective for plating of all typesincluding copper plating, nickel plating, cadmium plating, chromiumplating, zinc plating, gold plating and tin plating. The plating filmcan also be formed to uniform thickness in a short time.

[0116] Electro-degreasing and electropolishing are important aspreprocessing for the above surface treatments. The present inventionalso makes these processes more efficient for example by boosting theprocessing speed.

[0117] Electroforming is the deposition of a plating such as copper,nickel or iron on the base piece.

[0118] Conventional electroform plating yielded a plating film with athickness of approximately 100 micrometers and required a long period oftime. Besides requiring a long period of time, conventional electroformplating also had the problem that many irregularities appeared in thefilm thickness. However by applying this invention to that process, theupper electrical current density limit can be increased from theconventional 30 A/dm² to approximately 60 A/dm². This increase serves toimprove production efficiency by 40 percent. Another benefit is that theuniformity of the film thickness is ±2 μm for 300 μm and provides anextremely high quality product. Electroform plating with the method ofthis invention can be applied for example to manufacturing productionmolds for optical disks.

BRIEF DESCRIPTION OF THE DRAWINGS

[0119]FIG. 1 is a cross sectional view of the liquid treatment apparatususing the insulated vibration-stirring apparatus of the presentinvention;

[0120]FIG. 2 is an enlarged cross sectional view of the attachmentportion for mounting the vibrating rod onto the vibrating member;

[0121]FIG. 3 is an enlarged cross sectional view of a variation of theattachment portion for mounting the vibrating rod onto the vibratingmember;

[0122]FIG. 4 is a graph showing the relation of the vibration height ofthe vibrating vane to the vibrating vane vertical direction;

[0123]FIG. 5 is an enlarged fragmentary cross sectional view showing thevicinity of the electrical insulation area on the vibrating rod;

[0124]FIG. 6 is a perspective view showing the electrical insulationarea on the vibrating rod;

[0125]FIG. 7 is a flat view showing the electrical insulation area onthe vibrating rod;

[0126]FIG. 8 is a side view showing the insulated vibration-stirringapparatus of the present invention;

[0127]FIG. 9 is a cross sectional view of the liquid treatment apparatususing the insulated vibration-stirring apparatus of the presentinvention;

[0128]FIG. 10 is a cross sectional view of the liquid treatmentapparatus using the insulated vibration-stirring apparatus of thepresent invention;

[0129]FIG. 11 is an enlarged cross sectional view of the attachmentportion for mounting the vibrating vane onto the vibrating rod;

[0130]FIG. 12 is a cross sectional view showing the vicinity of thevibrating vane;

[0131]FIG. 13 is a cross sectional view of the liquid treatmentapparatus using the insulated vibration-stirring apparatus of thepresent invention;

[0132]FIG. 14 is a cross sectional view of the liquid treatmentapparatus using the insulated vibration-stirring apparatus of thepresent invention;

[0133]FIG. 15 is a perspective enlarged fragmentary view of theinsulated vibration-stirring apparatus of the present invention;

[0134]FIG. 16 is a fragmentary cross sectional view of the liquidtreatment apparatus used in the insulated vibration-stirring apparatusof the present invention;

[0135]FIG. 17 is a fragmentary side view of the liquid treatmentapparatus using the insulated vibration-stirring apparatus of thepresent invention;

[0136]FIG. 18 is a fragmentary side view of the liquid treatmentapparatus using the insulated vibration-stirring apparatus of thepresent invention;

[0137]FIG. 19 is a fragmentary cross sectional view of the liquidtreatment apparatus using the insulated vibration-stirring apparatus ofthe present invention;

[0138]FIG. 20 is a drawing showing the electrode support vanes;

[0139]FIG. 21 is a cross sectional view of the surface treatmentapparatus using the insulated vibration-stirring apparatus of thepresent invention;

[0140]FIG. 22 is a cross sectional view of the surface treatmentapparatus using the insulated vibration-stirring apparatus of thepresent invention;

[0141]FIG. 23 is a flat view of the surface treatment apparatus usingthe insulated vibration-stirring apparatus of the present invention;

[0142]FIG. 24 is a flat view of the surface treatment apparatus usingthe insulated vibration-stirring apparatus of the present invention;

[0143]FIG. 25 is a flat view of the surface treatment apparatus usingthe insulated vibration-stirring apparatus of the present invention;

[0144]FIG. 26 is a frontal view of the electrode support member;

[0145]FIG. 27 is a flat view showing for reference, a structure of thesurface treatment apparatus using the vibration-stirring apparatus;

[0146]FIG. 28 is a cross sectional view of the surface treatmentapparatus using the insulated vibration-stirring apparatus of thepresent invention;

[0147]FIG. 29 is a cross sectional view of the surface treatmentapparatus using the insulated vibration-stirring apparatus of thepresent invention;

[0148]FIG. 30 is a cross sectional view of the surface treatmentapparatus using the insulated vibration-stirring apparatus of thepresent invention;

[0149]FIG. 31 is a perspective view of the cylindrical titanium net caseconfiguring the electrode member;

[0150]FIG. 32 is a cross sectional view of the surface treatmentapparatus using the insulated vibration-stirring apparatus of thepresent invention;

[0151]FIG. 33 is a fragmentary cross sectional view of the insulatedvibration-stirring apparatus of the present invention;

[0152]FIG. 34 is a fragmentary perspective view of the liquid treatmentapparatus using the insulated vibration-stirring apparatus of thepresent invention;

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0153] The embodiments of the present invention are described next indetail while referring to the drawings. Members or sections in thedrawings having the same functions are assigned the same referencenumerals.

[0154]FIG. 1 is a cross sectional view of the liquid treatment apparatususing the insulated vibration-stirring apparatus of the presentinvention.

[0155] In FIG. 1, the treatment tank (electrolysis tank) is denoted bynumeral 10A. The processing fluid 14 is stored in this treatment tank.Reference numeral 16 is the vibration stirring apparatus. The vibrationstirring apparatus 16 is comprised of a base 16 a clamped to a supportbed 40 installed via anti-vibration rubber (vibration cushioning member)41 on the upper edge of treatment tank 10A, a coil spring 16 b as avibration absorbing material with the bottom edge clamped to the base, avibration member 16 c clamped to the top edge of that coil spring, avibration motor 16 d installed on that vibration member, the top edge ofa vibrating rod upper section 16 e′ installed on the vibration member 16c, a vibrating rod lower section 16 e installed by way of an insulationarea 16 e″ on the lower part of that vibrating rod upper section, and avibrating vane 16 f unable to rotate and installed at multiple levels ata position immersed in the processing fluid 14 at the lower half of thevibrating rod lower section. The vibrating rod is comprised of thevibrating rod upper section 16 e′, insulation area 16 e″, vibrating rodlower section 16 e. A vibration generating means is comprised of avibration motor 16 d, and a vibration member 16 c and that vibrationgenerating means is linked to the vibrating rod. A rod-shaped guidemember 43 can be installed towards the top and bottom and clamped to thebase 16 a within the coil spring 16 b.

[0156] Besides general-purpose mechanical vibration motors, thevibration generating means for the vibration stirring apparatus of thepresent invention may also utilize magnetic oscillating motors and airvibration motors, etc. A resilient piece such as rubber may also be usedalong with or instead of the coil spring 16 b as the vibration straindispersion member. Vibration stain dispersion members may be made ofrubber plate or laminations (layers) of rubber plates and metal plates.These laminated pieces may be joined by adhesive applied between thepieces or may simply be overlapped onto each other. When using theselaminated pieces, pieces capable of covering the top opening of thetreatment tank 10A can be used so that the treatment tank 10A is sealedtight. In such cases however, a seal should be installed between thevibrating rod and laminated piece so that the vibrating rod passingthrough the laminated piece can move up and down.

[0157] A transistor inverter 35 for controlling the frequency of thevibration motor 16 d is installed between the vibration motor 16 d andthe power supply 136 for driving that motor 16 d. The power supply 136is for example 200 volts. The drive means for this vibration motor 16 dcan also be used in the other embodiments of the present invention.

[0158] The vibration motors 16 d vibrate at 10 to 500 Hertz undercontrol of the inverter 35. These motors 16 preferably vibrate at 20 to200 Hertz and more preferably vibrate at 20 to 60 Hertz. The vibrationgenerated by the vibration motors 16 d is transmitted to the vibratingvane 16 f by way of the vibrating member 16 c and the vibrating rods (16e, 16 e′, 16 e″). In the description hereafter, for the purposes ofsimplicity, only the reference number 16 e is used to represent thevibrating rods.

[0159]FIG. 2 is an enlarged cross sectional view of the attachmentportion 111 for mounting the vibrating rod 16 e onto the vibratingmember 16 c. The nuts 16 i 1, 16 i 2 are fit from the top side ofvibration member 16 c, by way of the vibration strain dispersion member16 g 1 and washer 16 h, onto the male screw section formed at the topend of vibrating rod 16 e. The nuts 16 i 3, 16 i 4 are fit by way of thevibration strain dispersion member 16 g 2 from the bottom side (onto thescrew section) of the vibration member 16 c.

[0160] The vibration strain dispersion member 16 g 1, 16 g 2 areutilized as a vibration stress dispersion means made for example fromrubber. The vibration strain dispersion member 16 g 1, 16 g 2 can bemade from a hard resilient piece for example of natural rubber, hardsynthetic rubber, or plastic with a Shore A hardness of 80 to 120 andpreferably 90 to 100. Hard urethane rubber with a Shore A hardness of 90to 100 is particularly preferably in view of its durability andresistance to chemicals. Utilizing the vibration stress dispersion meansprevents vibration stress from concentrating on the near side of thejunction of vibrating member 16 c and the vibrating rod 16 e, and makesthe vibrating rod 16 e more difficult to break Raising the vibrationfrequency of the vibrating motors 16 d to 100 Hertz or higher isparticularly effective in preventing breakage of the vibrating rod 16 e.

[0161]FIG. 3 is an enlarged cross sectional view of the attachmentportion 111 for mounting the vibrating rod 16 e onto the vibratingmember 16 c. This variation differs from the attachment portion of FIG.2, only in that the vibration strain dispersion member 16 g 1 is notinstalled on the top side of the vibration member 16 c, and in thatthere is a spherical spacer 16 x between the vibration member 16 c andthe vibration strain dispersion member 16 g 2. In all other respectsthis variation is identical.

[0162] In FIG. 1, the vibrating vane 16 f is damped with vibrating vanedamp members 16 j comprised comprised of nuts fitting onto male screwsinstalled on the bottom side of the vibrating rod 16 e. The tip edges ofthe vibrating vane 16 f vibrate at the necessary frequency in theprocessing liquid. This vibration causes the vibrating vane 16 f togenerate a ripple or “flutter” to occur towards the edges of the vanefrom the attachment portion on the on the vibrating rod 16 e. Theamplitude and frequency of this vibration will vary according to themotor 16 d. However these are basically determined according to theinteraction between the processing liquid 14 and the force dynamics ofthe vibration transmission path. In the present embodiment, theamplitude (vibration width) is preferably 0.1 to 30 millimeters and thefrequency is 200 to 12,000 times per minute.

[0163] Resilient metal plate or plastic plate (electrically conductiveon at least its surface) may be used as the vibrating vane 16 f. Asatisfactory thickness range for the vibrating vane 16 f differsaccording to the vibration conditions and viscosity of the electrolyticfluid 14. However, during operation of the vibration-stirring means 16,the vibrating vanes should be set so the tips of the vibrating vanes 16f provide an oscillation (flutter phenomenon) for increasing thestirring (or agitating) efficiency, without breaking the vibrating vane.If the vibrating vane 16 f is made from metal plate such as stainlesssteel plate, then the thickness can be set from 0.2 to 2 millimeters. Ifthe vibrating vane 16 f is made from plastic plate then the thicknesscan be set from 0.5 to 10 millimeters. The vibrating vane 16 f anddamping member 16 j can be integrated into one piece. Integrating theminto one piece avoids the problem of having to wash away electrolyticfluid 14 that penetrates into the junction between the vibrating vane 16f and damp member 16 j and hardens and adheres there.

[0164] The material for the metallic vibrating vane 16 f may betitanium, aluminum, copper, steel, stainless steel, a ferromagneticmetal such as ferromagnetic steel, or an alloy of these metals. Thematerial for the plastic vibrating vane 16 f may be polycarbonate, vinylchloride resin, polyprophylene, etc.

[0165] The extent of the “flutter phenomenon” generated by the vibratingvane that accompanies the vibration of vibrating vane 16 f within theelectrolytic fluid 14 will vary depending on the vibration frequency ofthe vibration motors 16 d, the length of the vibrating vane 16 f(dimension from the tip of clamping member 16 j to the tip of vibratingvane 16 f), and thickness, and viscosity and specific gravity of theelectrolytic fluid 14, etc. The length and thickness of the “fluttering”vibrating vane 16 f can be best selected based on the applied frequency.By making the vibration frequency of vibrating motor 16 d and thicknessof vibrating vane 16 f fixed values, and then varying the length ofvibrating vane 16 f, the extent of vibrating vane flutter will be asshown in FIG. 14. In other words, the flutter will increase up to acertain stage as the length m of vibrating vane 16 f is increased, butwhen that point is exceeded, the extent F of the flutter will becomesmaller. As can be understood from the graph, at a certain length theflutter will be almost zero and if the vane is further lengthened theflutter increases and this process continuously repeats itself.

[0166] Preferably a length L₁ shown as the No. 1 peak or a length L₂shown as the No. 2 peak is selected for the length of the vibrating vane16 f. Here, L₁ or L₂ can be selected as needed, according to whether onewants to boost the path vibration or the flow. When L₃ shown here as theNo. 3 peak was selected, the amplitude will tend to diminish howeverthis has the advantage that the surface area can be increased whenutilizing the vibrating vane as an electrode.

[0167] The vibrating vanes 16 f can be installed on a single or multiple(for example, 2 to 8 levels) on the vibrating rod 16 e. The number ofvibrating vane levels depends on the performance of the vibration motorand the quantity of processing fluid 14. The number of levels can beselected as needed according to the vibration-sting that is required.

[0168]FIG. 5 is an enlarged fragmentary cross sectional view showing thevicinity of the electrical insulation area 16 e″ on the vibrating rod.FIG. 6 is a perspective view showing the electrical insulation area 16e″ on the vibrating rod. FIG. 7 is a flat view of that electricalinsulation area.

[0169] The electrical insulation area 16 e″ can be formed for examplefrom plastic or rubber. The electrical insulation area 16 e″ is astructural part on the vibrating rod so preferably material should beselected that is able to sufficiently transmit the vibration of thevibrating motor without breaking due to the vibration and also have goodinsulating properties. In view of these conditions hard rubber is mostpreferable. One potential material is hard polyurethane rubber. If themember comprised only of insulation material has insufficient strengththen a member made only of insulating material can for example beaugmented with metal to obtain the required mechanical strength.

[0170] More specifically, the electrical insulation area 16 e″ may bemade from a cylindrical insulating member (optional shape such as apolygon) manufactured from hard rubber as shown in the drawing.Insertion holes 124, 125 are formed in the center upper and lowersections to allow insertion respectively of the vibrating rod uppersection 16 e′ and a vibrating rod lower section 16 e. These holes do notallow passage all the way through (are not open on both sides) and theblocked section of the hole therefore functions as an insulatingsection.

[0171] If these upper and lower insertion holes allow passage all theway through (open on both sides) then insulation material can be filledinto the hole spaces where the rod is not inserted or a space allowingsufficient insulation can be established so that the vibrating rod uppersection 16 e′ and a vibrating rod lower section 16 e do not makecontact. The cylindrical insulation material for the insertion holes124, 125 serves to couple the vibrating rod upper section 16 e′ andvibrating rod lower section 16 e. This coupling may be made with asetscrew (For example, cutting the male screws on the top edge ofvibrating rod lower section 16 e and the bottom edge of vibrating rodupper section 16 e′, cutting the female screws in insertion holes 124,125, and joining both of them. Also applying a washer on the joint iffurther needed, and damping with a machine screw.) or joining them withadhesive. Any other kind of structure may be used for this section aslong as it achieves the object of the present invention.

[0172] For example, when the vibrating rod has a diameter of 13millimeters, the insulation area 16 e″ has a length (height) L forexample of 100 millimeters, the outer diameter r₂ for example is 40millimeters, and the inner diameter r₂ of the insertion holes 124, 125is 13 millimeters.

[0173] As shown in FIG. 1 and in FIG. 5, an electrical line 127 connectsto the upper section of vibrating rod lower section 16 e from directlybelow the electrical insulation area 16 e″. This electrical line 127 isconnected to a power supply 126 and an electrical line 127 connects thetreatment tank 10A to the power supply 126 as shown in FIG. 1. When thevibrating rod lower section 16 e, vibrating vane clamp member 16 j andvibrating vane 16 f are made from an electrically conductive member suchas metal, then an electrical current flow between the vibrating rodlower section 16 e, vibrating vane damp member 16 j and vibrating vane16 f and treatment tank 10A, based on a voltage applied across vibratingrod lower section 16 e and treatment tank 16 e from the power supply 126by way of the electrical lines 127 and 128. Vibration-stirring toprocess the processing liquid 14 is performed in this way. The powersupply voltage may be alternating current voltage, direct currentvoltage or pulse voltage as desired. The power supply voltage valuevaries according to the desired processing and may for example by 1 to15 volts. The power supply current value also varies according to thedesired processing and may for example be 0.5 to 100 amperes.

[0174] An electrode member connected to the electrical line 127 may beinstalled inside the treatment tank 10A. In this way, power can beconducted by the processing liquid 14 to achieve even higher electricalcurrent density among the vibrating rod lower section 16 e, vibratingvane clamp member 16 j, vibrating vane 16 f serving as electrodes. Also,one more vibration-stirring apparatus identical to the presentembodiment can be installed within the treatment tank 10A, and byconnecting the lower section of that vibrating rod to the electricalline 127, power can be conducted by the processing liquid 14 among thevibrating rod lower section 16 e, vibrating vane clamp member 16 j,vibrating vane 16 f of the two vibration-stirring apparatus. Thedistance between the electrode members (for example, vibrating vane 16 futilized as one electrode, and treatment tank 10A utilized as the otherelectrode, or dedicated anode and cathode members) installed to makecontact as electrodes in the processing liquid 14 for conducting power,may for example be 20 to 400 millimeters with no danger of electricalshorts occurring during processing.

[0175] The processing of the processing liquid 14 may for example bedisinfecting of the liquid by conducting electrical power. In otherwords, germs tend to propagate in the plating when the chlorine ions areremoved from the plating liquid, speeding up the deterioration of theplating liquid. However the propagation of these germs can be preventedby applying electrical power. This method may also be utilized fordisinfecting water for washing, tableware, vegetables and fruits ordisinfecting beverages such as water or milk. Other processing of theprocessing liquid 14 may for example be electrolysis to separate forexample water into oxygen and hydrogen.

[0176] When the processing liquid used is for example, diluted chlorine(water-soluble), then the cathode material in this processing may beplatinum, platinum alloy, platinum type metal or an alloy sheath. Whenfor example the processing liquid is caustic alkali (water-soluble) thenthe cathode material may be nickel, nickel alloy, iron, iron alloy,carbon steel, or stainless steel, etc.

[0177] In the present embodiment, the vibrating rod upper section 16 e′is electrically insulated from the vibrating rod lower section 16 e bythe insulation area 16 e″ so there is no effect on the vibrating motors16 d from the power conducting by way of the vibrating rod lower section16 e. Also in this embodiment, the insulation area 16 e″ has heatinsulating properties so the vibrating rod lower section 16 e is alsoheat-insulated from the vibrating rod upper section 16 e′, so there islittle effect from the temperature of the processing liquid 14 on thevibrating motors 16 d. Therefore there is no heat deterioration on thevibrating motors 16 d regardless of whether the processing fluid 14 is ahigh temperature or a low temperature.

[0178] Also in the present embodiment, an electrode member connected tothe power supply 126 is installed within the treatment tank 10A withoututilizing the vibrating vane of the insulated vibration-stirringapparatus as an electrode. So an insulation area 16 e″ is present, evenwhen conducting power to the processing fluid 14 using the electrodemember. There is therefore no effect on the vibrating motors 16 d fromsupplying electrical power to the processing fluid 14.

[0179]FIG. 8 is a side view showing another embodiment of the insulatedvibration-stirring apparatus of the present invention. This embodimentdiffers from the embodiment of FIG. 1 only in that the electrode supportvanes 16 f are installed on the vibrating rod lower section 16 e atmutually alternate positions versus the vibrating vane 16 f. Theelectrode support vane 16 f is electrically connected to the vibratingrod lower section 16 e and functions as one electrode when applyingpower to the processing fluid 14 and therefore does not require avibration-stirring function. The purpose of the electrode support vane16 f is to increase the electrode surface area and to decrease the gapbetween that electrode and the electrode on the opposite side so thesize (surface area) of the electrode support vane 16 f is preferablylarger than the vibrating vane 16 f. Also, as shown in the drawing, thetip (right edge) of the electrode support vane 16 f″ preferablyprotrudes farther to the right than the tip (right edge) of thevibrating vane 16 f.

[0180] The electrode support vane 16 f″ is preferably installed at aposition midway between a vibrating vane and a vibrating vane on thevibrating rod. However the installation position is not limited to thisposition and may be installed at a position in proximity to a vibratingvane from above or below as long as there is not drastic reduction inthe vibration-stirring effect. The electrode support vane 16 f″ can beinstalled on the vibrating rod lower section 16 e in the same way as thevibrating vane 16 f was installed.

[0181] The material of the electrode support vane 16 f″ may be anymaterial allowing use as an electrode. However since it must vibratealong the vibrating rod it must be sufficiently tough to withstandvibration. A conductive piece capable of use as a vibrating vane may forexample by made of titanium (platinum plating can be deposited on itssurface) or stainless steel (platinum plating can be deposited on itssurface). The vibrating vane 16 f need not always be an electricallyconductive material when using the electrode support vane 16 f″, and maybe made of plastic.

[0182]FIG. 9 and FIG. 10 are cross sectional views of the liquidtreatment apparatus in the insulated vibration-string apparatus of thepresent invention. FIG. 11 is an enlarged cross sectional view of theattachment portion for mounting the vibrating vane 16 f onto thevibrating rod 16 e.

[0183] In this embodiment, the vibrating vanes are installed on twovibrating rods. As shown in FIG. 11, the vibrating vane clamp members 16j are installed on both the upper and lower sides of each vibrating vane16 f. Spacer rings 16 k are installed at intervals in the adjacentvibrating vanes 16 f by way of the vibrating vane clamp members 16 j orsetting the spacing. A nut 16 m is screwed on to the vibrating rod 16 eformed as a male screw (with or without spacer rings 16 k) on the upperside of the topmost section of vibrating vane 16 f, and the lower sideof the bottom-most section of the vibrating vane 16 f as shown in FIG.10. As shown in FIG. 11, the breakage of the vibrating vane 16 f can beprevented by installing a resilient member sheet 16 p as the vibrationdispersion means made from fluorine plastic or fluorine rubber betweeneach vibrating vane 16 f and clamping member 16 j. The resilient membersheet 16 p is preferably installed to protrude outwards somewhat fromthe clamping member 16 j in order to further enhance the breakageprevention effect of the vibrating vane 16 f. This resilient membersheet 16 p can also be used in the same way in the other embodiments.The vibrating rod 16 e and the vibrating vane 16 f are electricallyconnected.

[0184] As shown in the figure, the lower surface (press contact surface)of the upper side of clamping member 16 j is formed with a protrudingsurface, and the upper surface (press contact surface) of the lower sidedamping member 16 j is formed with a recessed surface. The section ofthe vibrating vane 16 f compressed from above and below by the dampingmember 16 j is in this way forced in a curved shape, and the tip of thevibrating vane 16 f forms an angle, relative to the horizontal surface.This α angle can be set to −30 degrees or more and 30 degrees or less,and preferably is set −20 degrees or more and 20 degrees or less. The αangle in particular, is −30 degrees or more and −5 degrees or less, oris 5 degrees or more and 30 degrees or less, and preferably is set to−20 degrees or more and −10 degrees or less, or to 10 degrees or moreand 20 degrees or less. The α angle is 0 if the clamping member 16 j(press contact) surface is flat. The α angle need not be the same forall the vibrating vanes 16 f. For example, the lower one to two vanes onvibrating vane 16 f may be set to a minus value (in other words, facingdownwards: facing as shown in FIG. 11) and all other vanes on vibratingvane 16 f set to a plus value (in other words facing upwards: thereverse of the value shown in FIG. 11). When using electrode supportvanes these can be set to face downward or face upward at an appropriateangle the same as the vibrating vane 16 f.

[0185]FIG. 12 is a cross sectional view showing the vicinity of thevibrating vane 16 f. The section of the vibrating vane 16 f protrudingout from the damping member 16 j contributes to generating a vibrationflow motion. This protruding section has a width D₁ and length of D₂. Inthis embodiment, the vibrating vanes are installed across the multiplevibrating rods. The vibration surface area of the vibration vanes cantherefore be made sufficiently large. The surface area utilized as theelectrode can also be made large.

[0186] In this embodiment, a rod-shaped upper guide member clamped tothe vibrating member 16 c and a rod-shaped lower guide member clamped tothe base 16 a are installed at suitable intervals within the coil spring16 b.

[0187] Though not shown in the drawing, the present embodiment utilizesa power supply 126 (for processing) and an electrical line 128 asdescribed for FIG. 1.

[0188] In this embodiment also, the electrode support vanes are used inthe same way as the embodiment for FIG. 8.

[0189]FIG. 13 is a cross sectional view of another embodiment of theliquid treatment apparatus using the insulated vibration-stirringapparatus of the present invention. In this embodiment of thevibration-stirring apparatus 16, the vibration motor 16 d is installedoutside the treatment tank 10A, and the vibration member 16 c extendstowards the treatment tank 10A.

[0190] Though not shown in the drawing, the present embodiment alsoutilizes a power supply 126 (for processing) and an electrical line 128as described for FIG. 1.

[0191]FIG. 14 is a cross sectional view of another embodiment of theliquid treatment apparatus using the insulated vibration-stirringapparatus of the present invention. In this embodiment, the samevibration motor 16 d, vibration member 16 c, vibrating rod upper section16 e′, and the electrical insulation area 16 e″ are installed as a seton both sides of the treatment tank 14. The vibrating rod lower section16 e is formed in the shape of a square open on the left side, and thetwo perpendicular sections are installed on the two correspondinginsulation areas 16 e″. The top edges of the two perpendicular sectionof 16 e are respectively connected by way of the electrical insulationareas 16 e″ to the vibrating rod upper section 16 e′. The vibrating vane16 f is installed nearly perpendicular to the horizontal section of thevibrating rod lower section 16 e. The vibrating vanes 16 f may beinstalled tilted relative to the perpendicular direction, the same aspreviously described.

[0192] Though not shown in the drawing, the present embodiment alsoutilizes a power supply 126 (for processing) and an electrical line 128as described for FIG. 1.

[0193] In this embodiment for FIG. 13 and the embodiment for FIG. 14,the electrode support vanes are used in the same way as the embodimentfor FIG. 8.

[0194]FIG. 15 is a perspective enlarged fragmentary view showing avariation of the insulated vibration-stirring apparatus of the presentinvention. In this adaptation (or variation), a piece having a surfacemade from titanium oxide functioning as a photo-activated catalyst isused as the vibrating vane clamp member 16 j for the vibrating vane 16 fFurthermore, a ferromagnetic member (magnet) 16 j′ is fit into a sectionof that clamp member 16 j. Therefore, ultraviolet (UV) light emittedfrom the ultraviolet lamp 51 irradiates the clamp member 16 j. At thesame time, while power is applied to the processing liquid by way of thevibrating rod 16 e, the clamp member 16 j and vibrating vane 16 f, thesame as in the above embodiment, the liquid treatment apparatus forvibration-stirring of the processing liquid, renders a disinfectanteffect by magnetism generated from the ferromagnetic member 16 j′, adisinfectant effect based on the photo-activated catalyst of clampmember 16 j and a disinfectant effect rendered by the conduction ofelectricity. An ample amount of processing liquid is also supplied tothe vibrating rod 16 e, clamp member 16 j, ferromagnetic member 16 j′and vibrating vanes 16 f and extremely efficient disinfecting of theprocessing liquid is achieved.

[0195] One technique for forming the surface made for example fromtitanium oxide is composite plating containing fine particles (particlesof 5 μm or less) such as TiO₂. The surface having these kind ofphotocatalytic properties can be formed not only on the clamp member 16j but also on members (For example, vibrating vane 16 f and inner tankmember 61 in the embodiment of FIG. 34 described later on.) requiringthe same disinfectant processing.

[0196] Though not shown in the drawing, the present embodiment alsoutilizes a power supply 126 (for processing) and an electrical line 128as described for FIG. 1.

[0197]FIG. 34 is a fragmentary perspective view showing a variation ofthis kind of liquid treatment apparatus. In this variation, multipleinner tank members 61 having a surface made for example from titaniumoxide and having photocatalytic properties are affixed in parallel by asupport member 60. These adjacent inner tank members 61 are enclosed byoptical fibers 53. These optical fibers 53 are mutually installed inparallel and an exposure section is formed for example by surfaceroughing on the side surfaces. Ultraviolet light supplied from anultraviolet light source not shown in the drawing is emitted from oneend of the of the optical fiber 53. Ultraviolet light from the opticalfiber exposure section in this way irradiates the adjacent inner tankmembers 61, power is conducted to the processing liquid by way of thevibrating rod 16 e and clamp member 16 j and vibrating vane 16 f in thesame manner as the above embodiments. The disinfectant effect based onphotocatalytic activation of the inner tank members 61 is renderedsimultaneously with the disinfectant effect from power conduction. Anample amount of processing liquid is also supplied to the vibrating rod16 e, clamp member 16 j, and vibrating vanes 16 f as well as the innertank members 61 and extremely efficient disinfecting of the processingliquid is achieved. The electrical lines 127 and a (processing) powersupply 126 connecting the vibrating rod lower section 16 e andelectrical insulation area 16 e″ are not shown in the drawing but areinstalled the same as the above embodiments.

[0198] In this embodiment, ultraviolet light is irradiated onto theinner tank members 61 from an extremely close position so that thedisinfectant effect is strong even when the transmittance of theultraviolet light in the processing liquid is low (for example when theprocessing liquid is milk.)

[0199] Though not utilizing the insulated vibration stirring apparatusof the present invention, similar disinfectant processes are disclosedin the Japanese patent applications JP-A No. 271189/2001 and JP-A No.102323/2002 of the present inventors.

[0200]FIG. 16 is a fragmentary cross sectional view of anotherembodiment of the liquid treatment apparatus using the insulatedvibration-sing apparatus of the present invention. FIG. 17 is afragmentary side view of that liquid treatment apparatus.

[0201] In this embodiment, the vibrating vane 16 e and clamp member 16 jmechanically connecting the two vibrating rod lower sections 16 e aregrouped into two sets. A first set is electrically connected to thevibrating rod lower section 16 e and the second set is electricallyconnected to the other vibrating rod lower section 16 e. Voltage isapplied across these two sets to conduct electrical power to theprocessing liquid 14 and for the required processing.

[0202] In other words, in FIG. 16, the odd-numbered vibrating vanes 16 fand damp members 16 j are electrically connected from the upper sidewith the vibrating rod lower section 16 e on the right side. However,the vibrating rod lower section 16 e on the left side is electricallyinsulated by the insulation bushing 16 s and insulation washer 16 t.However, the even-numbered vibrating vanes 16 f and clamp members 16 jare electrically connected from the upper side with the left sidevibrating rod lower section 16 e but are electrically insulated from theright side vibrating rod lower section 16 e by the insulation bushing 16s and the insulation washer 16 t.

[0203] The odd-numbered vibrating vanes 16 f and clamp members 16 j fromthe upper side are therefore made the first set; and the even-numberedvibrating vanes 16 f and clamp members 16 j from the upper side are madethe second set. The electrical wire 127 connecting to the left side ofvibrating rod lower section 16 e, and the electrical wire 127 connectingto the right side of vibrating rod lower section 16 e, apply thenecessary power from the power supply not shown in the drawing. Powercan in this way supplied across the first set and second set to theprocessing liquid 14. The insulation bushing 16 s and insulation washer16 t are omitted from the drawing in FIG. 17.

[0204] In this embodiment, the electrical insulation area 16 e″ isinstalled between the vibration rod 16 e and the vibration member 16 ccomprising the vibration generating means. In other words, theelectrical insulation area 16 e″ in this embodiment also functions asthe attachment portion 111 for installing the vibrating rod 16 e on thevibration member 16 c.

[0205] In this embodiment, when using direct current for applyingvoltage to the processing liquid 14, the vibrating vane 16 f forming theanode preferably has a surface of titanium coated with platinum.Preferably titanium is used on the vibrating vane 16 f forming thecathode.

[0206] In this embodiment, power to the vibration-stirring apparatus isonly for liquid processing so the apparatus can be made compact. Alsothe vibrating vanes 16 f can incorporate the functions of two types ofelectrodes and so from that viewpoint the device can be made morecompact.

[0207]FIG. 18 is a fragmentary side view showing another embodiment ofthe liquid treatment apparatus using the insulated vibration-stirringapparatus of the present invention.

[0208] In this embodiment, an anode member 16 f″ is used instead of theupper side even-numbered vanes 16 f in the embodiments of FIG. 16 andFIG. 17. This anode member 16 f″ does not contribute to the vibrationstirring and extends only to the right side of the drawing. The anodemember 16 f″ preferably utilizes lath-webbed titanium (platinum platingon surface). A cathode member 16 f″ is added by way of the spacers 16 uas the upper side odd-numbered vanes 16 f. This cathode member 16 f″also does not contribute to the vibration stirring and extends only tothe right side of the drawing. Preferably, titanium plate for example isused as the cathode member 16 f″.

[0209] In this embodiment, the anode member 16 f″ and cathode member 16f″ are utilized separate from the vibrating vane 16 f so there is morefreedom in selecting the electrode material.

[0210]FIG. 19 is a fragmentary cross sectional view of anotherembodiment of the liquid treatment apparatus using the insulatedvibration-stirring apparatus of the present invention.

[0211] In the present embodiment, two insulated vibration-stirringapparatus are installed in the treatment tank 10A. The electrode supportvanes 16 f′ of one insulated vibration-string apparatus are positionedbetween the electrode support vanes 16 f′ of the other adjacentinsulated vibration-stirring apparatus. In this way, one of the twoinsulated vibration-stirring apparatus can be used as the anode and theother used as the cathode. This method allows installing the large size(surface area) anode and cathode in close mutual proximity to eachother. This method also allows a drastic improvement in the electricalcurrent density.

[0212] In the present embodiment, insulating tape 16 fa is preferablyaffixed to the outer circumferential surfaces on both sides of theelectrode support vanes 16 f′ as shown in FIG. 20 to prevent electricalshorts from occurring due to contact between the electrode support vanes16 f′ of the two insulated vibration-stirring apparatus.

[0213]FIG. 33 is a fragmentary cross sectional view of anotherembodiment of the insulated vibration-stirring apparatus of the presentinvention. In the present embodiment, the electrical insulation area 16e″ is used as a heat insulation area. A heat exchange medium injectorsection 130 and heat exchange extraction section 132 are installed onthe lower side (Namely, the side installed with vibrating vanes notshown the in drawing, using the insulation area 16 as a reference.) ofthe electrical insulation area 16 e″ on the vibrating rod lower section16 e. These heat exchange medium injector section 130 (or injector 130),heat exchange extraction section 132 (or extractor 132) and connectedheat exchanger path 131 are installed on this vibrating rod lowersection 16 e. Further, by making the heat exchange medium connect fromthe injector 130 by way of the heat exchanger path 131 to the extractor132, the heat insulation effect of the electrical insulation area 16 e″is rendered whether the processing liquid is a high temperature or a lowtemperature. The effects of heat on the vibrator generating meansincluding the vibration motor can therefore be prevented

[0214] In this embodiment, when heat insulating by using the insulationarea 16 e″ heat insulation dimensions are preferably larger than thedimensions for electrical insulation. A fin-shaped heat dissipationplate can also be formed on the outer circumference of electricalinsulation area 16 e″. When the processing liquid is cool (lowtemperature), a heater can be installed on the vibrating rod lowersection 16 e instead of having a heat exchange medium flow to the path131.

[0215] Next, an embodiment of the surface treatment apparatus of thepresent invention is shown. Even in the following specific examples, thesurface treatment apparatus of this invention can comprise processingliquid from the liquid treatment apparatus of the above embodiments asthe processing fluid and also the product for processing can besubstituted for one electrode member.

[0216]FIG. 21 and FIG. 22 are cross sectional views of an embodiment ofthe surface treatment apparatus using the insulated vibration-stirringapparatus of the present invention.

[0217] In the present embodiment, insulated vibration-stirring apparatusare installed respectively on the both right and left ends of thetreatment tank 10A. The above embodiments are utilized for theseinsulated vibration-stirring apparatus. The electrode support vanes 16f′ in particular are used here. The processing liquid 14 is storedwithin the treatment tank 10A, and the processing product ART isinstalled within that processing liquid. This processing product ART issupported while hung from the support means 80 and power can beconducted to it from the support means 80.

[0218] When the product for processing is on the anode side such as foranodic oxidation, then an anode bus-bar is used as the support means 80as shown in the figure. The cathode bus-bar is supplied by theelectrical line 128 connecting to the anode of the (processing) powersupply. The cathode of the power supply on the other hand, connects byway of an electrical line 127 to the vibrating rod lower sections 16 eof the two vibration-stirring apparatus. In contrast, when the productfor processing is on the cathode side such as during plating, then thecathode bus-bar is used as the support means 80. This cathode bus-barconnects to the cathode of the processing power supply by way of anelectrical line 128, and the anode of this power supply connects to thevibrating rod lower sections 16 e of the two vibration-stirringapparatus by way of the electrical line 127.

[0219] The processing power supply need only supply direct current andpreferably supplies normal low-ripple direct current. However powersupplies using direct current having other types of waveforms may alsobe utilized.

[0220] Among the various pulse waveforms for example, a rectangularwaveform pulse is preferable view of its improved energy efficiency.This type of power supply (power supply apparatus) can create voltageswith rectangular waveforms from an AC (alternating current) voltage.This type of power supply further has a rectifier circuit utilizing forexample, transistors and is known as a pulse power supply. This powersupply or rectifier device may be a transistor regulated power supply, adropper type power supply, a switching power supply, a siliconrectifier, an SCR type rectifier, a high-frequency rectifier, aninverter digital-controller rectifier device, (for example, the PowerMaster made by Chuo Seisakusho (Corp.)), the KTS Series made by SanshaDenki (Corp.), the RCV power supply made by Shikoku Denki Co., a meansfor supplying rectangular pulses by switching transistors on and off andcomprised of a switching regulator power supply and transistor switch, ahigh frequency switching power supply (using diodes to change thealternating current into direct current, and then add a 20 to 30 KHzhigh frequency waveform, and with power transistors apply transforming,once again rectify the voltage, and extract a smooth (low-ripple)output), a PR type rectifier device, a high-frequency control typehigh-speed pulse PR power supply (for example, a HiPR Series (ChiyodaCorp.), a thyristor reverse parallel-series connection type, etc.

[0221] The current waveforms are now described next. Selection of thecurrent waveform for plating and anodic oxidation is important in orderto acheive high-speed plating or anodic oxidation and to improve thecharacteristics of the plating film or anodic oxidized film. The voltageand current conditions required for electrical plating or anodicoxidizing differ for example, according to the type of anodic oxidationor plating and the composition of the processing liquid (solution) andtreatment tank dimension. These conditions cannot be limited to specificfigures. However, a plating voltage for example of 2 to 15 volts ofdirect current can cover most conditions. The industry standard forrated power supply output consists of four types: 6 volts, 8 volts, 12volts and 15 volts. The rated voltage can be adjusted to a lower voltageso preferably a rated power supply is selected that has the voltagevalue needed for plating with extra capacity. The industry standards forrated output current are approximately 500 amperes, 1,000 amperes, 2,000amperes up to 10,000 amperes. A production order is made for othervoltages. The best strategy is determining the required voltage capacityof the power supply by multiplying the current density of the product tobe plated by the surface area of the plated surface of the product to beplated and then selecting a standard power supply that matches thisrequired voltage capacity.

[0222] The pulse wave is essentially has a width that is sufficientlysmall relative to the period. However this is not a strict definition.The pulse waveform also includes waveforms other than square waves. Theoperating speed of devices using pulse circuits has become faster andpulse widths up to the nanosecond (10⁻⁹s) range can be handled. As thepulse width becomes narrower, maintaining a sharp shape on the risingedge and falling edge of the pulse becomes difficult. Maintaining thepulse edges is difficult because the pulse contains high frequencycomponents. The type of pulse waves include sawtooth waves, ramp waves,triangular waves, composite waves, and rectangular waves, (square waves)etc. In the processing in this invention square waves are preferred inparticular because of their electrical efficiency and smoothness, etc.

[0223] Typical pulse plating power supplies include switching regulatortypes direct current power supplies and transistor-switched supplies. Inthe transistor-switched type, the transistors turn on and off at highspeed to supply pulses with a rectangular waveform.

[0224] Besides direct current electrolysis, anodic oxidation can alsouse pulse electrolysis. Pulse electrolysis utilizing the currentreversal method has many advantages including high-speed, improved filmquality, and improved coloring.

[0225] The current reversal function is a basic feature of pulseelectrolysis power supplies so a set of two pulse supplies are connectedtogether to have mutually opposite polarity. However, the efficiency ofthis method deteriorates according to usage conditions so applying it topulse electrolysis using large capacity power supplies in industrialapplications is difficult compared to pulse plating. Applying the 3PRtype rectifier device however has the advantages of being highlypractical because of efficiency, cost, compactness and lightweight, etc.

[0226] The pulse electrolysis waveform for the thyristor reverseparallel-series connection type applies the principle of the PR typerectifier with reverse-parallel connected thyristors. The output voltagewaveform is therefore the same as the thryistor rectifier device. Thenormal power conduction ratio is electronically controlling the waveformripple frequency by the pulse string and so can be variably set toapproximately 3.3 milliseconds in the 50 Hertz band or 2.8 millisecondsin the 60 Hertz band.

[0227] The processing product ART is maintained at a distance of 20 to400 millimeters from the tip of the electrode support vane 16 f. Themain surface (both sides of the plate member) to be processed isinstalled to face the tip of the electrode support vane 16 f.

[0228] In the processing in this embodiment, the product ART serves asone electrode. The vibrating vane 16 f and electrode support vane 16 felectrically connected to the vibrating rod lower section 16 e of theinsulated vibration-stirring apparatus serve as the other electrode.Therefore, gas bubbles generated by gas on the electrode surface oradhering to it can be speedily removed by the flow motion of theprocessing liquid 14 based on the vibration-stirring action of thevibrating vanes 16 f. The electrical current efficiency is thereforeimproved and an electrical reaction can be fully boosted in theprocessing fluid.

[0229] In this variation of the embodiment, yet another electrode member(for example, the metal to be plated during plating processing) can alsobe jointly utilized as the other electrode. In these cases, theelectrode member to be used is connected to the power supply to have thesame polarity as the insulated vibration-stirring apparatus. In thisway, the specified desired amount of current can be maintained and theservice life of the vibrating vane and electrode support vane can belengthened. Also in this variation, an ordinary vibration stirringapparatus can be used instead of the insulated vibration-stirringapparatus (or without the vibrating rod of the insulatedvibration-stirring apparatus connecting to the power supply), the otherelectrode can be utilized exclusively for the electrode member. Avariation of this type can be used in the same in the followingembodiment.

[0230]FIG. 23 is a flat view showing the structure of the surfacetreatment apparatus for the insulated vibration-stirring apparatus usingthe present invention. This embodiment is for example applicable toprocessing of electrodeposition paint (pigment).

[0231] In FIG. 23, the liquid electrodeposition paint/coatingconstituting the processing liquid 14 is stored inside the treatmenttank 10A. The product support means 80 constituted by the suspensionconveyor is installed on the treatment tank 10A. A processing productART such as an automotive component is hung from the hanger comprisingthat support means 80. The processing product ART is immersed in theprocessing liquid 14 in the treatment tank 10A. Two insulatedvibration-stirring apparatus 16, the same as described in the aboveembodiment are installed on both sides of the movement path of theprocessing product ART. In the present embodiment, the two insulatedvibration-stirring apparatus 16 are installed on one side, at positionscorresponding to the dimensions of the processing product ART. In otherwords, the present embodiment is equivalent to the embodiments for FIG.21 and FIG. 22 with two units having a common treatment tank.

[0232] The power supply for the electrodeposition coating applies avoltage across the hanger of the support means 80 and the insulatedvibration-stirring apparatus 16 to perform electrodeposition coating.The non-processing product ART is maintained at a distance from 20 to400 millimeters from the tip of the electrode support vane 16 f′.

[0233]FIG. 24 is a flat view of another embodiment of the surfacetreatment apparatus using the insulated vibration-stirring apparatus ofthe present invention. This embodiment is used for example forelectrodeposition coating. This embodiment is basically the same as theembodiments of FIG. 21 and FIG. 22 (The drawing shows that only thepolarity of the voltage applied to the processing product ART isdifferent. However this polarity is set as needed to match the type ofprocessing.). In the electrodeposition processing, a voltage of adifferent polarity is applied to the processing product ART according tothe anion electrodeposition device or cation electrodeposition device.In the present invention, the cation electrodeposition device isparticularly preferred for use on the anode side of the insulatedvibration-stirring apparatus 16.

[0234]FIG. 25 is a flat view of another embodiment of the surfacetreatment apparatus for the insulated vibration-stirring apparatus ofthe present invention. This embodiment is used for example forelectrodeposition coating.

[0235] The present embodiment is equivalent to the embodiment of FIG. 24added with a support means 82 for an electrode member 84 applied withvoltage of the same polarity as the insulated vibration-stirringapparatus 16. The support means 80 for the processing product ART is forexample a cathode bus-bar. The support means 82 for the electrode member84 is for example an anode bus-bar. The electrode member 84 is forexample a lath-webbed titanium (preferably with platinum deposited onthe surface) electrode member. FIG. 26 is a frontal view of the lath webelectrode support member. Two suspension holes are formed in the uppersection for hanging. The area from the center section to the lowersection is formed in a web shape. This web shape is immersed in theprocessing liquid. The electrode member 84 is installed in parallel withthe processing product ART and installed between the insulatedvibration-stirring apparatus 16 and processing product ART.

[0236]FIG. 27 is a flat view showing for reference, the structure of thesurface treatment apparatus using the vibration-string apparatus. Inthis example, the vibration stirring apparatus is not the insulatedtype. The processing product ART and the electrode member 85 aremutually installed in parallel but are not installed facing thevibration-stirring apparatus 16.

[0237]FIG. 28 is a cross sectional view of another embodiment of thesurface treatment apparatus using the insulated vibration-stirringapparatus of the present invention. This embodiment is used for examplein anodic oxidation processing. The present embodiment is basicallyequivalent to the embodiments of FIG. 21 and FIG. 22 added with asupport means 82 for an electrode member 84 applied with voltage of thesame polarity as the insulated vibration-stirring apparatus 16. However,electrode support vane are not used. The support means 80 for theprocessing product ART is for example an anode bus-bar. The electrodemember 84 comprising the support means 82 is for example an anodebus-bar. This support means 82 for electrode member 84 is for example atitanium lath web electrode member.

[0238]FIG. 29 and FIG. 30 are cross sectional views showing thestructure of the surface treatment apparatus using the insulatedvibration-stirring apparatus of the present invention. This embodimentis applicable for example to processing by electroform plating. Thisembodiment is basically equivalent to the embodiment of FIG. 25 with theinsulated vibration-stirring apparatus and electrode member removed onthe right side of the processing product ART. Electrode support vaneshowever are not utilized in this embodiment. Also, multiple metal balls(nickel balls, copper balls, etc.) fill the inside of the cylindricaltitanium web case as shown in FIG. 31 are used as the electrode member86. The case is maintained to face horizontally.

[0239]FIG. 32 is a cross sectional view showing the structure of anotherembodiment of the surface treatment apparatus using the insulatedvibration-stirring apparatus of the present invention. This embodimentis used for example for plating processing. This embodiment is basicallythe same as the embodiment of FIG. 25. However, the electrode memberidentical to the embodiments of FIG. 29 and FIG. 30 is utilized as theelectrode member 86.

[0240] In the respective liquid treatment apparatus of FIG. 1, FIG. 9,FIG. 13, and FIG. 14, the product for processing held by the supportmeans is connected to the electrical line 128 and that product forprocessing is used as one electrode. By then immersing this product inthe processing liquid 14, the liquid treatment apparatus of theseembodiments can be utilized as surface treatment apparatus for theproduct.

[0241] The present invention is described next with the followingembodiments. The present invention however is not limited to theseembodiments.

[0242] [First Embodiment] (Milk Sterilizer)

[0243] Milk was sterilized using the liquid treatment apparatusdescribed for FIG. 34. The processing conditions were as follows.

[0244] Insulated vibration-stirring apparatus: is installed on bothsides of the inner tank member 61 of FIG. 34 as described in FIG. 16 andFIG. 17.

[0245] Vibration motor: 200 volts (3-phase)×150 watts, vibrationfrequency: 42 Hertz

[0246] Vibrating vane: Cathode side is titanium. Anode side is platinumplating on the titanium surface.

[0247] Processing power supply voltage: 4.5 volts

[0248] Processing current: 3.5 amperes

[0249] Treatment tank: W300×L700×H350 millimeters

[0250] Processing fluid: Using a tryptiquese growth medium theintestinal bacteria (colon bacillus) was cultured for 24 hours at 35° C.After propagation, a turbid bacteria medium of 60 liters of milk withinthe treatment tank “contained 22,000 colon bacillus per liter of milk”.

[0251] After irradiating with ultraviolet light, conducting power andvibration-stirring (agitation), the results as shown in the followingtable 1 were obtained. TABLE 1 Processing time Living colon bacillus perliter  3 minutes 30 or less per milliliter  5 minutes 30 or less permilliliter 10 minutes None detected

[0252] To measure the living bacteria, 40 milliliters of processed milkwas extracted from 4 locations within the treatment tank as samples formeasurement. These were measured by the viable count method and pourplate method.

[0253] [Second Embodiment] (Electrodeposition Painting)

[0254] Cation electrodeposition coating of automotive parts wasperformed using the insulated vibration-stirring apparatus described inFIG. 21 and FIG. 22, as the insulated vibration-stirring apparatus 16for the surface treatment apparatus (electrodeposition coating device)described in FIG. 23.

[0255] A tank made of steel with an inner lining of plastic was used asthe treatment tank (electrodeposition tank) 10A. A processing liquid 14(liquefied electrodeposition coating) consisting of synthetic fattysoluble emulsion, pigment paste, and water was filled into this tank. Anegative electrode hanger was affixed to the electrically insulatedsuspension conveyor 80 in the tank. The automotive part (processingproduct ART) was hung from it and used as the negative electrode. Asshown in FIG. 21 and FIG. 22, the insulated vibration-stirring apparatuscontains two vibrating rods and, a vibrating vane of titanium platedwith platinum (thickness 0.5 mm, D₁=250 mm and D₂=55 mm as shown in FIG.12, a tilt angle α=15 degrees as shown in FIG. 11) and an electrode vaneof titanium plated with platinum (thickness equivalent to 0.5 mm, D₁=250mm and D₂=150 mm as shown in FIG. 12, a tilt angle α=15 degrees as shownin FIG. 11) connected to the positive electrode. These vibrating vaneswere vibrated at 45 Hertz by a vibrating motor at an amplitude (vanewidth) of 2 mm, and number of vibration of 1500 times per minute. Atotal of four insulated vibration-stirring apparatus 16 are installed asshown in FIG. 23 with two units each facing each other while enclosingthe processing product ART.

[0256] The insulated vibration-stirring apparatus utilizes 200 volts,three-phase vibration motors of 250 watts. Cylindrical material of hardpolyurethane as described in FIG. 5 through FIG. 7 was utilized for theelectrical insulation area on the vibrating rod.

[0257] Electricity conducted to the vibrating rods was 250 volts by wayof an inverter and an electrical current density of 20 A/dm². Theminimum gap between the tip of the electrode support vane and theautomotive part was set at 100 millimeters. The immersion time that theautomotive part was in the liquid electrodeposition pigment (coating)was 3 minutes.

[0258] An electrodeposition coating film of approximately 40 micrometerswas obtained as a result of this process.

[0259] In the comparison sample on the other hand, electricity was notconducted to the vibrating rod. A set of four electrode plates werepositioned at nearly the same distance as from the automotive part tothe vibrating rod and electricity was conducted to the electrode plates.Further, the immersion time was six minutes and the coating thicknesswas 20 micrometers when the vibration stirring apparatus was driven andelectrodeposition coating performed.

[0260] Consequently the above shows that applying electricity to thevibrating rods shortened the electrodeposition time by approximatelyone-fourth

[0261] [Third Embodiment] (Electrodeposition Coating)

[0262] The insulated vibration-stirring apparatus of the thirdembodiment does not use electrode support vanes. The vibrating vane havea thickness of 0.5 millimeters, D₁=250 mm and D₂=170 mm as shown in FIG.12 and a tilt angle α=15 degrees as shown in FIG. 11. A titanium lathweb electrode plate (electrode member) with platinum plating wasinserted between all insulated vibration-stirring apparatus andautomotive part as described using FIG. 26. These electrode plates wereanodes of the same polarity utilizing vibrating rods and vibrating vanesof the vibration-stirring apparatus. The gap between the tip of thevibrating vane and the lath web electrode plate was 50 millimeters. Theminimum distance between the lath web electrode plate and automotivepart was 100 millimeters. In other words, the positional relationship ofthe insulated vibration-stirring apparatus, the lath web electrode plateand the processed part was the same as shown in FIG. 28.

[0263] Electrodes having the same polarity can in this way be installedinstead of using electrode support vanes. Results obtained were similarto those of the second embodiment.

[0264] [Fourth Embodiment] (Electrodeposition Coating)

[0265] The fourth embodiment utilizes the same insulatedvibration-string apparatus as the third embodiment. Here, anionelectrodeposition coating of the automotive part was performed asdescribed for the surface treatment apparatus (electrodeposition coatingapparatus) described in FIG. 23. In a treatment tank made of iron, acopolymer of lindseed oil and maleic acid was neutralized with ethanolamino. Water and a solvent comprised of cellosolve acetate butylate wasadded, and an anion electrodeposition coating adjusted to a non-volatileportion of 10 percent was also added. The automotive part used as theanode was hung from the suspension conveyor. The treatment tankconstituted the anode (positive electrode) and the insulatedvibration-stirring apparatus served as the cathode (negative electrode).The gap between the tip of the vibrating vanes of the insulatedvibration-stirring apparatus serving as the cathode and the automotivepart serving as the anode was set at 100 millimeters. A lath webelectrode plate (See FIG. 26; thickness 3.0 millimeters, web portionthickness 1.5 millimeters, one mesh opening angle length of 10millimeters, and other angle length of 20 millimeters) of titanium wasinstalled on the side opposite the automotive part of the insulatedvibration-stirring apparatus. The gap between the rear end of thevibrating vane of the insulated vibration-stirring apparatus and thelath web electrode plate was 50 millimeters (In other words, a distanceof 50 millimeters between the lath web electrode plate and edge of sideopposite the tip of the vibrating vane facing the automotive part.). Thegap between the lath web electrode plate and treatment tank was set at100 millimeters.

[0266] The vibration motors of the insulated vibration-stirringapparatus were driven at 45 Hertz by an inverter. The vibrating vaneshad an amplitude (vibration width) of 2 millimeters and were made tovibrate at a frequency of 1,800 times per minute. A direct currentvoltage of 200 volts was applied across the cathode and anode (positiveand negative electrodes) by the power supply and electrodepositioncoating performed at room temperature. Electrodeposit coating wasperformed at an electrical current density of 10 A/dm² applied in thefirst stage for one minute, and an electrical current density of 15A/dm² applied in the second stage for one minute. When the product withthe electrodeposited coating obtained in this way was sintered at 160°C. after washing, an electrodeposit coating 30 micrometers thick andsuperior resistance to rust was obtained.

[0267] [Fifth Embodiment] (Electrodeposition Coating)

[0268] The installation of the fourth embodiment had the configurationof automotive part-insulated vibration-stirring apparatus-titanium lathweb electrode plate-electrodeposition tank. However the presentembodiment has the configuration of automotive part-stainless steel webelectrode plate (electrode member)-insulated vibration-stirringapparatus-electrodeposition tank. The gap between the automotive productand the stainless steel web electrode plate is 100 millimeters. The gapbetween the stainless steel web electrode plate and vibrating vane frontedge is 50 millimeters. The gap between the vibrating vane rear end andelectrodeposition tank is 100 millimeters.

[0269] Though the processing results from this embodiment were somewhatinferior to those of the fourth embodiment, the results were largelysatisfactory.

[0270] [Sixth Embodiment] (Electrodeposition Coating)

[0271] The insulated vibration-stirring apparatus shown in FIG. 14 wasutilized. The small part serving as the product for processing wasplaced in a narrow rotating basket (plastic barrel). The narrow rotatingbasket periphery was installed facing the vibrating vane. The gapbetween the vibrating vane and rotating basket was 100 millimeters. Thevibrating vane was of stainless steel and had a thickness of 0.5millimeters and a D₁=250 mm and D₂=170 millimeters as shown in FIG. 12.

[0272] A liquid electrodeposition paint material including alkyd resinwater-soluble plastic emulsion, pigment paste, water and other materialsis filled into the tank. The product for processing in the interior ofthe rotating basket is the cathode (negative electrode) and thevibrating vane is the anode (positive electrode) and cationelectrodeposition painting/coating is performed. The electrical currentdensity in this processing was 15 A/dm².

[0273] Speedy and uniform electrodeposition coating/painting of thesmall part without flaws can in this way be achieved.

[0274] [Seventh Embodiment] (Electrodeposition Coating)

[0275] In this embodiment, the following processes (1) through (4) wereperformed as preprocessing on a one meter square steel plate

[0276] (1) Degreasing: Using the vibration-sting apparatus (vibrationmotor with frequency of 40 Hertz), degreasing processing was performedfor two minutes at 50 to 60° C. using a weak alkali degreasing fluid.

[0277] (2) Washing: Using the vibration-stirring apparatus (vibrationmotor with frequency of 40 Hertz) processing was performed with waterfor two minutes at 40 to 50° C.

[0278] (3) Distilled water washing: Processing was performed for twominutes with deionized water at room temperature and a resistance of5×10⁵ ohms or more.

[0279] (4) Water cutoff-air drying: Processing performed for 5 minutesat 130 to 140° C. and the following electrodeposition coating wasperformed on the steel plate obtained from the preprocessing.

[0280] Electrodeposition tank: Steel lined tank (600 liters of liquid)

[0281] Electrodeposition material: Water-soluble primer type emulsionpaint neutralized with epoxy adduct of grade 4 amino.

[0282] Liquid temperature: 30° C.

[0283] Type and installation of vibration-stirring apparatus:

[0284] (a) A 150 watt×200 volt (three-phase) insulatedvibration-stirring apparatus (vibrating vane [titanium with platinumcoating)] and electrode support vane [titanium with platinum coating)]and processing product were installed as shown in FIG. 25. The distancefrom the tip of the electrode support vane to the steel plate serving asthe processing product was 100 millimeters. The processing product wasthe cathode (negative electrode) and the vibrating vanes and electrodesupport vanes of the insulated vibration-stirring apparatus were theanode (positive electrode). Using a rectifier device, 150 volts wasapplied and the electrical current density was 30 A/dm².

[0285] (b) Here, a titanium lath web electrode plate (of FIG. 26) withplatinum plating was installed between the insulated vibration-stirringapparatus of (a) and processing product as shown in FIG. 25. The gapbetween the steel plate comprising the processing product and the lathweb electrode plate was 100 millimeters. The gap between the lath webelectrode plate and tip of the electrode support vane of the insulatedvibration-stirring apparatus was 50 millimeters. The processing productwas the cathode (negative electrode) and the lath web electrode plateand vibrating vanes and electrode support vanes were the anode (positiveelectrode). Using a rectifier device, 150 volts was applied and theelectrical current density was 30 A/dm².

[0286] (c) This configuration is for comparison purposes. The processingproduct and electrode member and vibration-stirring apparatus wereinstalled as shown in FIG. 27. In this installation, the steel platecomprising the processing product and the electrode member were facingeach other but the vibrating vanes of the vibration-stirring apparatuswere installed at a right angle to them, regardless of how theprocessing product and electrode member were facing. In the conventionaltype stirring apparatus, only the efficient agitation (mixing) was thenumber one priority. No thought was given to placing the vibrating vanesdose to the processing product or installing the vibrating vanes andprocessing product to face each other. Rather the vibration-stirringapparatus was installed at a position as far away as possible from theprocessing product and the processing product and electrode member wereinstalled at a right angle to the vibrating vane so as not to interferewith the flow of the fluid. Unlike the installations of (a) and (b)however, in this installation there is no need for a metal web-shapedelectrode member. Also, the vibration-stirring apparatus need not be aninsulated type. Here, the gap between the processing product andelectrode member was 400 millimeters. The vibrating vane was stainlesssteel, the thickness was 0.4 millimeters and D₁=180 mm and D₂=50millimeters as shown in FIG. 12 length shown by first peak in FIG. 4).The processing product was the cathode (negative electrode) and theelectrode member was the anode (positive electrode). The electricalcurrent density was 3 A/dm².

[0287] Electrodeposition painting (coating was performed at atemperature of 30° C. in all of the above systems (a), (b) and (c).Results obtained from electrodeposition of these sample plates are shownin Table 2. The vibration-stirring apparatus was used both thepreprocessing and postprocessing for the electrodepositionpainting/coating. TABLE 2 (a) (b) (c) Coating time (min.) 1 1 3Electrodeposited film 25 ± 1 25 ± 1 25 ± 3 thickness (μm) AppearanceSatisfactory Satisfactory A few gas Satisfactory holes Salt-water sprayOK after 200 OK after 200 Rust occurred test hours hours after 96 hoursDurability test No No Rust occurred abnormalities abnormalities after 96hours after 700 hours after 700 hours

[0288] Remarks)

[0289] Salt-water spray test: JIS-K-5400 Cut off a sample test piece,seal the periphery, make an X cut mark

[0290] Durability test (with Weatherow meter): JIS-K-5400 Cut off asample test piece and seal the periphery.

[0291] [Eighth Embodiment] (Anodic Oxidation)

[0292] Anodic oxidation generally has the problem that the time requiredis too long compared to the pre and postprocesses.

[0293] Therefore in this eighth embodiment, the apparatus shown in FIG.21 and FIG. 22 were used. The insulated vibration-stirring apparatusused here is described as below.

[0294] Vibration motor: 200 volts (3-phase)×150 watts,

[0295] vibration frequency: 50 Hertz

[0296] Vibrating vane: Six vanes made of titanium, the thickness was 0.4millimeters and D₁=180 mm and D₂=150 millimeters as shown in FIG. 12(length shown by second peak in FIG. 4).

[0297] Electrode support vane: Five vanes made of titanium.

[0298] An aluminum piece (#2017) with dimensions of 100×100×2 mm wasutilize as the processing product. The processing liquid was adjustedusing sulfur as the chemical (200 grams per liter) and general-purposealamite [embodiment 7-1] and hard alamite [embodiment 7-2] were formed.

[0299] As comparison samples, general-purpose alamite and hard alamitewere formed in layout of FIG. 27 using a conventional typevibration-stirring apparatus that was not the insulated type.

[0300] The anodic oxidation processing conditions and results obtainedare shown in Table 3 and Table 4. TABLE 3 Embodiment 7-1 Comparisonsample Voltage [V] 19 19 Temperature [° C.] 21 21 Electrical currentdensity 30 4 [A/dm²] Processing time [min.] 3 30 Film thickness [μm] 2427 Hardness [HV] 350 250 Appearance No microporosity Slightmicroporosity Anti-rust test [h] 86 48 Luster Satisfactory Deterioration

[0301] Remarks)

[0302] Film thickness test: JIS-H-8680 Eddy current measurement

[0303] Hardness pass/fail: JIS-H-8882 Vickers hardness meter (HV)

[0304] Anti-rust test: Alamite JIS-K-5400

[0305] Salt-water spray test (white rust)

[0306] Hardness alamite: JIS-H-8681

[0307] Corrosion durability: CASS test TABLE 4 Embodiment 7-2 Comparisonsample Voltage [V] 21 21 Temperature [° C.] 5 5 Electrical currentdensity 30 3 [A/dm²] Processing time [min.] 3 20 Film thickness [μm] 2422 Hardness [HV] 820 400 Appearance No microporosity Slightmicroporosity Anti-rust test [h] 2000 1200 Luster SatisfactoryDeterioration

[0308] Remarks)

[0309] Film thickness test: JIS-H-8680 Eddy current measurement

[0310] Hardness pass/Tail: JIS-H-882 Vickers hardness meter (HV)

[0311] Anti-rust test: Alamite JIS-K-5400

[0312] Salt-water spray test (white rust)

[0313] Hardness alamite: JIS-H-8681

[0314] Corrosion durability: CASS test

[0315] [Ninth Embodiment] (Anodic Oxidation)

[0316] This embodiment uses the apparatus of FIG. 28. An aluminum plate(#2017) with dimensions of 100×100×2 mm is used as the metal (productfor processing) piece for anodic oxidation. Titanium lath web electrodeplates were installed on both sides of the metal plate facing eachother. Insulated vibration-stirring apparatus were also installed onboth sides facing each other. The six vibrating vanes made of titanium,have a thickness of 0.4 millimeters and a D₁=180 mm and D₂=50millimeters as shown in FIG. 12 length shown by first peak in FIG. 4).The gap between the titanium lath web electrode plate and the vibratingvane was 50 millimeters. The gap between the titanium lath web electrodeplate and the aluminum plate was 100 millimeters.

[0317] Electrical power was not supplied via the insulatedvibration-stirring apparatus. The vibration motor was driven at 40Hertz, at a vibrating vane amplitude of 1.5 millimeter and a vibrated atspeed/frequency of 2,000 times per minute. The processing liquid wasadjusted using sulfuric acid (200 grams per liter) as the chemical toform general-purpose and hard alamite.

[0318] The processing results obtained from this embodiment weresomewhat inferior to those of the seventh embodiment, however there wasno microporosity and a largely uniform alamite was obtained.

[0319] The anodic oxidation processing conditions and results obtainedare shown below.

[0320] (First Results) General-Purpose Alamite

[0321] Voltage: 19 volts

[0322] Electrical current density: 20 A/dm²

[0323] Temperature: 21° C.

[0324] Processing time: 3 minutes

[0325] Film thickness: 16 μm

[0326] (Second Results) Hard Alamite

[0327] Voltage: 21 volts

[0328] Electrical current density: 20 A/dm²

[0329] Temperature: 5° C.

[0330] Processing time: 3 minutes

[0331] Film thickness: 16 μm

[0332] [Tenth Embodiment] (Anodic Oxidation)

[0333] Processing in this embodiment was performed the same as in theninth embodiment except that power was supplied via an insulatedvibration-stirring apparatus. The number of vibration/frequency of thevibration vanes was 1800 times per minute and the electrical currentdensity was 30 A/dm².

[0334] Results obtained were the largely the same as in the ninthembodiment.

[0335] [Eleventh Embodiment] (Anodic Oxidation of Magnesium)

[0336] A piece of magnesium alloy AZ91-D was utilized as the piece foranodic oxidation (processing product). Processes comprising:preprocessing/alkali immersion washing/washing (alkali anodeelectrolysis cleaning/washing) acid washing (neutralizing)/washing/acidprocessing/washing/anode processing/washing/dry were performed to obtainthe product.

[0337] The processing liquid for the acid processing was 85 percentphosphoric acid at 50 grams per liter. The usage temperature was 21° C.The composition of the processing liquid used in the anodic oxidationprocessing was as follows. potassium hydroxide 200 grams per liter sodium phosphate 50 grams per liter aluminum hydroxide 50 grams perliter

[0338] Anodic oxidation was performed using the apparatus as the eighthembodiment shown in FIG. 21 and FIG. 22.

[0339] A material for anodic oxidation the same as the eleventhembodiment was used as the comparison sample and anodic oxidationperformed by spark discharge of 250 volts.

[0340] Anodic oxidation processing conditions and results obtained areshown in Table 5. Embodiment 11 Comparison sample Voltage [V] 100 250Electrical current density 20 2 [A/dm²] Processing time [min.] 3 30 Filmthickness [μm] 25 25 Hardness [HV] 450 350 Appearance No microporosityMuch microporosity Anti-rust test No abnormalities Corrosion appearedafter 150 hours after 100 hours

[0341] Remarks)

[0342] Hardness pass/fail: JIS-H-8882 Vickers hardness meter (HV)

[0343] Appearance: Surface was visually inspected by microscope under500× magnification.

[0344] Anti-rust test: JIS-K-5400 Salt-water spray exposure test.

[0345] [Twelfth Embodiment] (Anodic Oxidation of Magnesium)

[0346] The composition of anodic oxidation processing liquid was asfollows. potassium hydroxide 165 grams per liter  potassium fluoride 35grams per liter sodium phosphate 35 grams per liter aluminum hydroxide35 grams per liter potassium permanganate 20 grams per liter

[0347] The processing was performed the same as the eleventh embodimentexcept for the above processing liquid. Results obtained were the sameas the eleventh embodiment.

[0348] [Thirteenth Embodiment] (Electroform Plating)

[0349] Electroform plating was performed on a circulate plate of SUSsteel for an optical disk with a diameter of 200 millimeters andthickness of 2 millimeters using the apparatus described in FIG. 29through FIG. 30. The insulated vibration-stirring apparatus contained avibration motor of 200 volts (three-phase)×250 watts. The vibratingvanes were made of titanium, having a thickness of 0.5 millimeters and aD₁=250 mm and D₂=55 millimeters as shown in FIG. 12 (length shown byfirst peak in FIG. 4). A large number of nickel balls with a diameter of25 millimeters were filled into the titanium web case of the electrodemember. The distance between the vibrating vanes and titanium web casewas 50 millimeters. The distance between the titanium web case andprocessing product was 100 millimeters. The vibration motor was drivenat 50 Hertz, at a vibrating vane amplitude of 2 millimeters and wasvibrated at a speed/frequency of 3,100 times per minute.

[0350] A nickel sulfamate bathe was used as the processing liquid andelectroforming performed according to the following points.

[0351] (1) Composition of nickel sulfamate bath

[0352] Nickel sulfamate crystals 600 grams per liter

[0353] Nickel chloride 5 grams per liter

[0354] Boric acid 40 grams per liter

[0355] Stress adjuster solution (naphthalin trisulfone soda) 0.5 to 3milliliters per liter

[0356] Pit inhibitor solution (sodium lauryl sulfate) 2 to 3 millilitersper liter.

[0357] (2) Processing temperature 50° C.

[0358] (3) Processing time 30 minutes

[0359] (4) Electrical current density 60 A/dm²

[0360] (5) Voltage 17 volts

[0361] (6) pH 4.5

[0362] Electroform plating utilizing an apparatus as described in FIG.27 and comprising an equivalent vibration-stirring apparatus exceptwithout insulation was performed for purposes of comparison.

[0363] Processing conditions and the results obtained are shown in Table6 below. TABLE 6 Thirteenth embodiment Comparison sample Processing time[min.] 30 60 Film thickness [μm] 300 ± 1 300 ± 10 Gas pit defects [%] 03 to 5

[0364] Gas pits are caused by hydrogen gas emitted during electrolysis.This hydrogen gas creates small holes in the electrodeposition surface.These small holes are flaws in the appearance of the plating surface andare the cause of product defects.

[0365] [Fourteenth Embodiment] (Plating)

[0366] In this embodiment, copper plating (in particular, plating of 50μm through holes) was performed on 100×100×1.5 millimeter epoxy plasticprinted circuit boards (processed product) that were subjected topreprocessing and electrical conduction processing using the platingapparatus described in FIG. 32.

[0367] The insulated vibration-stirring apparatus contained a 200 volts(three-phase) vibration motor×150 watts. The five vibrating vanes madeof titanium, having a thickness of 0.4 millimeters and a D₁=180 mm andD₂=50 millimeters as shown in FIG. 12 (length shown by first peak inFIG. 4). Four sets of eight copper-phosphorus balls arrayed verticallyand set facing the side were set inside the 250 mm×30 mm diametertitanium web case of the electrode member. The distance between thevibrating vanes and titanium web case was 50 millimeters. The distancebetween the titanium web case and processed product was 50 millimeters.

[0368] The vibration motor was driven at 50 Hertz, at a vibrating vaneamplitude/width of 2 millimeters and at a speed/frequency of 3000 timesper minute. The plating was performed as described below in the platingtank (725×400×450 mm).

[0369] (1) Composition of plating liquid

[0370] Sulfuric acid 190 grams per liter

[0371] Copper sulfate pentahydrate 70 grams per liter

[0372] Additive (brightener) 5 milliliters per liter

[0373] (2) Processing conditions

[0374] Plating bath fluid temperature 25° C.

[0375] Electrical current density 30 A/dm²

[0376] Processing time 5 minutes

[0377] Plating utilizing an apparatus as described in FIG. 27 andcomprising an equivalent vibration-stirring apparatus except withoutinsulation was performed for purposes of comparison.

[0378] Processing conditions and the results obtained are shown in Table7 below. TABLE 7 Fourteenth embodiment Comparison sample Voltage [V] 8 8Electrical current density 30 3 [A/dm²] Processing time [min.] 5 50 Filmthickness [μm] 33 ± 1 33 ± 3 Hardness [HV] 400 200 Appearance LusterSome luster Satisfactory leveling Deteriorated leveling

[0379] Remarks)

[0380] Film thickness test: JIS H-8680 Eddy current measurement

[0381] Hardness pass/fail: JIS-H-8882 Vickers hardness meter (HV)

[0382] [Fifteenth Embodiment] (Plating)

[0383] Copper plating of the printed circuit board was performed usingthe apparatus (However, the polarity is different from the apparatusshown in FIG. 21.) described in FIG. 21. The insulatedvibration-stirring apparatus was the same as the apparatus of thefourteenth embodiment except that it contains electrode support vanes.The dimensions of the electrode support vanes corresponding to D₁ ofFIG. 12 are the same but the dimensions corresponding to D₂ are twicethe size of the vibrating vanes. The electrode support vanes werecomprised of five vanes.

[0384] In all other respects the processing was the same as thefourteenth embodiment. The plating liquid was supplemented as needed.

[0385] The plating speed and the finished state was largely the same asthe fourteenth embodiment. However the plating for the through-holes wassuperior to the fourteenth embodiment.

[0386] [Sixteenth Embodiment] (Plating)

[0387] In this embodiment, processing was performed using a 5 percentpulse power supply with a frequency of 1 kHz and 8 volts of directcurrent. The plating of the 20 μm through-holes was one step betterlooking in appearance than the first embodiment. The plating was alsouniform and can be applied stably over a long period of time.

[0388] The invention configured as described above renders the followingeffects.

[0389] (1) Installing an insulated area on the vibrating rod of thevibration-stirring apparatus or between the vibrating rod and thevibration generating means renders the effect of opening up new fieldsfor utilizing the vibration-stirring apparatus.

[0390] (2) Using a heat-insulated area as the insulated area renders theeffect that the vibration-stirring apparatus can be used even foragitating high temperature or low temperature processing liquid.

[0391] (3) Electricity can be supplied to the vibration-stirringapparatus vibrating vanes and the electrode support vanes that areaffixed as needed. So the effect is rendered that the vibration stirringapparatus can possess the functions of at least one electrode forconducting electricity and the function of stirring or agitating forsurface treating the product for processing by conducting electricity orconducting electricity to the processing liquid.

[0392] (4) When the vibration-stirring apparatus of the presentinvention is used for surface treatment processing of the product byconducting electricity, electrical shorts do not occur even when thedistance between the product for processing and an electrode of oppositepolarity is short and electrical current made to flow. Furthermore,bubbles are not emitted from the product for processing or the electrodeso the effect is rendered that processing is performed stably and athigh speed compared to the conventional art and the efficiency of thesurface treatment processing is enormously improved. For example duringplating, the electrical current density in the conventional art of 3A/dm² can be increased to 20 to 30 A/dm² in the present invention; anelectrical current density of 30 A/dm² during electroform plating in theconventional art can be increased to 60 dm² in the present invention;and an electrical current density during anodic oxidation in theconventional art of 3 A/dm² can be increased to an 30 A/dm² in thepresent invention so the effect is rendered that each process isimproved.

[0393] (5) In particular, when electrode support vanes were added andutilized as electrodes with a polarity opposite that of the product forprocessing, the tip of the electrode support vane could be installedeven closer to the product for processing to render the effect that alarger electrical current density could be used in the processing.

[0394] (6) The present invention renders the effect that the surfaceobtained from surface treatment has excellent characteristics. Inparticular, the film that is formed has a uniform thickness andexcellent film quality characteristics.

[0395] (7) When the present invention is utilized for plating, theplating can be performed in a short time compared to conventionalmethods. Furthermore, the effect is rendered that the metal filmthickness can be finely crystallized onto the product for processing sothat a uniform, smooth and flat surface without pits can be formed.

[0396] (8) When the present invention is utilized for electrodeposition,the effect is rendered that a uniform electrodeposition film coating canbe formed with a small differential in film thickness between convex andconcave sections, even when coating product with complex, irregular(convex, concave) shapes.

[0397] (9) When the present invention is utilized for anodic oxidizingof light metals such as aluminum or magnesium, the effect is renderedthat processing time is greatly reduced and productivity is drasticallyimproved. Further, along with enormously improving the hardness of thefilm, a high quality product with no microporosity can simultaneously beobtained.

1. An insulated vibration-stirring apparatus comprising a vibrationgenerating means and, at least one vibrating rod for vibrating whilelinked to said vibration generating means, and at least one vibratingvane installed on said vibrating rod installed on a link section linkingsaid vibrating rod with said vibrating generating means, or on a sectionnearer the linking (connection) than the section where said vibratingvane is installed on said vibrating rod.
 2. An insulatedvibration-stirring apparatus according to claim 1, wherein saidinsulation area is a material comprised mainly of plastic and/or rubber.3. An insulated vibration-stirring apparatus according to claim 1,wherein said insulation area is an electrical insulation area, and anelectrical line is connected to said vibrating rod on the side of saidelectrical insulation area where said vibrating vanes are installed. 4.An insulated vibration-sting apparatus according to claim 3, comprisinga power supply connected to said electrical line.
 5. An insulatedvibration-stirring apparatus according to claim 3, wherein an electrodemember electrically connected to said electrical line by way of saidvibrating rod, is installed on said vibrating rod on the side of theelectrical insulation area where said vibrating vanes are installed. 6.An insulated vibration-stirring apparatus according to claim 5, whereinat least one vane of said vibrating vane functions as said electrodemember.
 7. An insulated vibration-stirring apparatus according to claim3, wherein electrode support vanes electrically connected to saidelectrical line by way of said vibrating rod, are installed on saidvibrating rod on the side of said electrical insulation area where saidvibrating vanes are installed.
 8. An insulated vibration-stirringapparatus according to claim 7, wherein said electrode support vanes areinstalled on said vibrating rod so that said electrode support vanepositions alternate with said vibrating vane positions.
 9. An insulatedvibration-stirring apparatus according to claim 7, wherein the surfacearea of said electrode support vanes is larger than the surface area ofsaid vibrating vanes, and the tips of said electrode support vanesprotrude farther than the tips of said vibrating vanes.
 10. An insulatedvibration-stirring apparatus according to claim 5, wherein a firstelectrode member and a second electrode member forming a pair of saidelectrode members are respectively connected to multiple said vibratingrods, and said first electrode member is electrically connected withsaid electrical line by way of at least one of said multiple vibratingrods, and said second electrode member is electrically connected withsaid electrical line by way of at least one other of said multiplevibrating rods.
 11. An insulated vibration-string apparatus according toclaim 10, wherein the gap between said first electrode member and saidsecond electrode member is maintained at 20 to 400 millimeters.
 12. Aninsulated vibration-stirring apparatus according to claim 10, whereinsaid vibrating vanes are installed on said multiple vibrating rods, andat least a portion of said vibrating vanes function as said firstelectrode member or as said second electrode member.
 13. An insulatedvibration-stirring apparatus according to claim 10, wherein each of themultiple vibrating vanes are installed on the multiple vibrating rods,and a portion of the multiple vibrating vanes function as said firstelectrode member and, another portion of the multiple vibrating vanesfunction as said second electrode member.
 14. An insulatedvibration-stirring apparatus according to claim 10, wherein saidelectrode support vanes are installed on the multiple vibrating rods onthe side of the electrical insulation area where said vibrating vanesare installed, and said electrode support vanes function as a said firstelectrode member or a said second electrode member.
 15. An insulatedvibration-stirring apparatus according to claim 10, wherein the multipleelectrode support vanes are installed on the multiple vibrating rods onthe side of said electrical insulation area where said vibrating vanesare installed, and a portion of said electrode support vanes function assaid first electrode member and, another portion of the multipleelectrode support vanes function as said second electrode member.
 16. Aninsulated vibration-stirring apparatus according to claim 1, whereinsaid insulation region is a heat insulation region, and a heat exchangemedium injector section and a heat exchange extraction section areinstalled on the side of said heat insulation area where said vibratingvanes are installed on said vibrating rod.
 17. A liquid treatmentapparatus comprising: an insulated vibration-stirring apparatuscontaining: a vibration generating means and, at least one vibrating rodfor vibrating while linked to said vibration generating means, and atleast one vibrating vane installed on said vibrating rod, and anelectrical insulation area installed on a link section linking saidvibrating rod with said vibrating generating means, or installed nearersaid linking (connection) than where said vibrating vane is installed onsaid vibrating rod; and further comprising a treatment tank for holdingsaid processing liquid, and a first electrode member and a secondelectrode member forming a pair, and a power supply for applying directcurrent, alternating current or pulsed voltages across said firstelectrode member and said second electrode member.
 18. A liquidtreatment apparatus according to claim 17, for maintaining a gap of 20to 400 millimeters between said first electrode member and said secondelectrode member.
 19. A liquid treatment apparatus according to claim17, wherein an electrical line is electrically connected to the side ofsaid electrical insulation area where said vibrating vanes are installedon said vibrating rod, and said first electrode member or said secondelectrode member are installed on said side of said electricalinsulation area where said vibrating vanes are installed on saidvibrating rod, and further are electrically connected to the powersupply by way of said vibrating rod and said electrical line.
 20. Aliquid treatment apparatus according to claim 19, wherein said vibratingvanes are electrically connected with said power supply by way of saidvibrating rod and said electrical line, and function as said firstelectrode member or as said second electrode member.
 21. A liquidtreatment apparatus according to claim 19, wherein said electrodesupport vanes electrically connected with said power supply by way ofsaid vibrating rod and said electrical line are installed on the side ofsaid electrical insulation area where said vibrating vanes are mountedon said vibrating rod, and function as said first electrode member or assaid second electrode member.
 22. A liquid treatment apparatus accordingto claim 19, comprising two insulated vibration-stirring apparatus; andsaid power supply applies a voltage across a said first electrode memberof one insulated vibration-stirring apparatus, and a second electrodemember of the other insulated vibration-stirring apparatus.
 23. A liquidtreatment apparatus according to claim 19, wherein said vibrating vanesare installed on the multiple vibrating rods, and each of said firstelectrode member and said second electrode member are installed on saidmultiple vibrating rods, and said first electrode member is electricallyconnected with said power supply by way of at least one of said multiplevibrating rods and said electrical line connected to said vibratingrods, and said second electrode member is electrically connected withsaid power supply by way of at least one of the other said multiplevibrating rods and said electrical line connected to said vibratingrods.
 24. A liquid treatment apparatus according to claim 23, wherein atleast one of said multiple vibrating rods and said vibrating vaneselectrically connected with said power supply by way of an electricalline connecting to said vibrating rod functions as said first electrodemember, and/or at least one of the other multiple vibrating rods andsaid vibrating vanes electrically connected with said power supply byway of an electrical line connecting to said vibrating rod, functions assaid second electrode member.
 25. A liquid treatment apparatus accordingto claim 23, wherein electrode support vanes are installed on saidmultiple vibrating rods on the side of said electrical insulation areawhere said vibrating vanes are installed, and at least one of saidmultiple vibrating rods and said electrode support vanes electricallyconnected with said power supply by way of an electrical line connectingto said vibrating rod, functions as said first electrode member, and/orat least one of the other multiple vibrating rods and said electrodesupport vanes electrically connected with said power supply by way of anelectrical line connecting to said vibrating rod, functions as saidsecond electrode member.
 26. A liquid processing method, wherein aprocessing liquid is filled into said treatment tank of a liquidtreatment apparatus according to claim 17, said vibrating vanes areimmersed in said processing liquid, and said vibrating vanes are made tovibrate while power is conducted across said first electrode member andsaid second electrode member by way of said processing liquid.
 27. Aliquid processing method according to claim 26, wherein a gap of 20 to400 millimeters is maintained between said first electrode member andsaid second electrode member.
 28. A liquid processing method accordingto claim 26, wherein said vibration generating means vibrates at afrequency of 10 to 500 Hz; said vibrating vanes have an amplitude ofvibration of 0.1 to 30 millimeters and further are made to vibrate at afrequency of 200 to 12,000 times per minute.
 29. A liquid processingmethod according to claim 26, wherein members installed on saidvibrating vane side of said electrical insulation region on saidvibrating rod in said vibration-stirring apparatus are utilized as atleast one of either said first electrode member or said second electrodemember.
 30. A liquid processing method according to claim 26, whereinsaid vibrating vanes are utilized as at least one of either said firstelectrode member or said second electrode member.
 31. A liquidprocessing method according to claim 26, wherein said electrode supportvanes installed on said vibrating vane side of said electricalinsulation region on said vibrating rod in said vibration-stirringapparatus are utilized as at least one of either said first electrodemember or said second electrode member.
 32. A liquid processing methodaccording to claim 26, wherein the method uses two insulatedvibration-stirring apparatus, a member installed on said vibrating rodof a first vibration-stirring apparatus is utilized as said firstelectrode member, and a member installed on another said vibrating rodof said second vibration-stirring apparatus is utilized as said secondelectrode member.
 33. A liquid processing method according to claim 26,wherein said vibrating vanes are installed on multiple said vibratingrods in said vibration-stirring apparatus, and members installed on saidvibrating vane side of said electrical insulation region on the multiplevibrating rods in said vibration-stirring apparatus are utilized as atleast one of either said first electrode member or said second electrodemember, and at least one among said multiple vibrating rods functioningas said first electrode member are electrically connected to said powersupply, and at least one among the other multiple vibrating rodsfunctioning as said second electrode member are electrically connectedto said power supply.
 34. A liquid processing method according to claim33, wherein said vibrating vanes are utilized as at least one of saidfirst electrode member and said second electrode member.
 35. A surfacetreatment apparatus comprising a treatment tank; a vibration-stirringapparatus (A) containing; a vibration generating means, at least onevibrating rod for vibrating while linked to said vibration generatingmeans, and at least one vibrating vane installed on said vibrating rod;an electrode member (B); and a holder for maintaining a product forprocessing (C) to allow electrical conduction, wherein said vibratingvanes, said electrode member (B) and said product for processing (C) areinstalled within said treatment tank to maintain a respective gap of 20to 400 millimeters.
 36. A surface treatment apparatus according to claim35, wherein said electrode member (B) or said product for processing (C)are installed to face the tip of said vibrating vane.
 37. A surfacetreatment apparatus according to claim 35, wherein said electrode member(B) is made from a porous plate piece, a web-shaped piece, abasket-shaped piece or a rod-shaped piece.
 38. A surface treatmentapparatus comprising: a treatment tank; a vibration-stifling apparatus(A′) containing; a vibration generating means, at least one vibratingrod for vibrating while linked to said vibration generating means, andat least one vibrating vane installed on said vibrating rod, and anelectrical insulation area installed on a link section linking saidvibrating rod and said vibration generating means or on a section nearerthe linking (connection) than the section where said vibrating vanes aremounted on said vibrating rod; and a holder for maintaining a productfor processing (C) to allow electrical conduction, wherein saidvibrating vanes, and said product for processing (C) are installedwithin said treatment tank to maintain a respective gap of 20 to 400millimeters.
 39. A surface treatment apparatus according to claim 38,wherein said product for processing (C) is installed to face the tip ofsaid vibrating vane.
 40. A surface treatment apparatus according toclaim 38, further comprising an electrode member (B), and said electrodemember (B) is installed within said treatment tank to maintain arespective gap of 20 to 400 millimeters with said vibrating vane andsaid product for processing (C).
 41. A surface treatment apparatusaccording to claim 40, wherein said electrode member (B) is made from aporous plate piece, a web-shaped piece, a basket-shaped piece or arod-shaped piece.
 42. A surface treatment apparatus according to claim38, wherein said insulation area of said insulated vibration-stirringapparatus (A′) is a material comprised mainly of plastic and/or rubber.43. A surface treatment apparatus according to claim 38, wherein on saidinsulated vibration-stirring apparatus (A′), an electrical line isconnected to said vibrating rod on the side of said electricalinsulation area where said vibrating vanes are installed.
 44. A surfacetreatment apparatus according to claim 38, wherein electrode supportvanes are installed on said vibrating rod on the side of said electricalinsulation area where said vibrating vanes are installed.
 45. A surfacetreatment apparatus according to claim 44, wherein said electrodesupport vanes are installed on said vibrating rod so that said electrodesupport vane positions alternate with said vibrating vane positions. 46.A surface treatment apparatus according to claim 44, wherein the surfacearea of said electrode support vanes is larger than the surface area ofsaid vibrating vanes, and the tips of said electrode support vanesprotrude farther than the tips said vibrating vanes.
 47. A surfacetreatment method of a surface treatment apparatus according to claim 35,wherein a processing liquid is filled into said treatment tank of asurface treatment apparatus, said vibrating vanes, said electrode member(B) and said product for processing (C) are immersed in said processingliquid, and one electrode member is set as said electrode member (B),and said product for processing (C) is set as said other electrode, andsaid vibrating vanes are made to vibrate while power is conducted acrossone electrode member and other said electrode member by way of saidprocessing liquid.
 48. A surface treatment method according to claim 47,wherein said surface treatment method is electrodeposition, anodicoxidation, electropolishing, electro-degreasing, plating or electroformplating or is preprocess or postprocess using these methods.
 49. Asurface treatment method according to claim 48, wherein saidelectrodeposition, anodic oxidation, electro-degreasing,electropolishing, plating or a preprocess or postprocess using thesemethods is performed at an electrical current density of 10 A/dm² ormore.
 50. A surface treatment method according to claim 48, wherein saidelectroform plating is performed at an electrical current density of 20A/dm² or more.
 51. A surface treatment method according to claim 47,wherein said vibration generating means vibrates at a frequency of 10 to500 Hz; said vibrating vanes have an amplitude of vibration of 0.1 to 30millimeters and further are made to vibrate at a frequency of 200 to12,000 times per minute.
 52. A surface treatment method according tosaid surface treatment apparatus of claim 38, wherein a processingliquid is filled into said treatment tank of a surface treatmentapparatus, said vibrating vanes and and said product for processing (C)are immersed in said processing liquid, said vibrating rod and saidvibrating vane electrically connected to said vibrating rod are set asone electrode, and further, said product for processing (C) is set asthe other electrode; and said vibrating vanes are made to vibrate whilepower is conducted across one electrode and other said electrode by wayof said processing liquid; and product for processing (C) is surfacetreated.
 53. A surface treatment method according to claim 52, whereinsaid electrode member (B) is installed within said treatment tank tomaintain a respective gap of 20 to 400 millimeters with said vibratingvane and said product for processing (C); and said electrode member (B)is utilized as the other electrode.
 54. A surface treatment methodaccording to claim 52, wherein the method is electrodeposition, anodicoxidation, electropolishing, electro-degreasing, plating or electroformplating or a preprocess or postprocess using these methods.
 55. Asurface treatment method according to claim 54, wherein saidelectrodeposition, anodic oxidation, electropolishing,electro-degreasing, plating or a preprocess or postprocess using thesemethods, or a preprocess or postprocess of electroform plating isperformed at an electrical current density of 10 A/dm² or more.
 56. Asurface treatment method according to claim 54, wherein said electroformplating is performed at an electrical current density of 20 A/dm² ormore.
 57. A surface treatment method according to claim 52, wherein saidvibration generating means vibrates at a frequency of 10 to 500 Hz; saidvibrating vanes have an amplitude of vibration of 0.1 to 30 millimetersand further are made to vibrate at a frequency of 200 to 12,000 timesper minute.